RESUMO
Reducing carbon dioxide (CO2) emissions urgently requires the large-scale deployment of carbon-capture technologies. These technologies must separate CO2 from various sources and deliver it to different sinks1,2. The quest for optimal solutions for specific source-sink pairs is a complex, multi-objective challenge involving multiple stakeholders and depends on social, economic and regional contexts. Currently, research follows a sequential approach: chemists focus on materials design3 and engineers on optimizing processes4,5, which are then operated at a scale that impacts the economy and the environment. Assessing these impacts, such as the greenhouse gas emissions over the plant's lifetime, is typically one of the final steps6. Here we introduce the PrISMa (Process-Informed design of tailor-made Sorbent Materials) platform, which integrates materials, process design, techno-economics and life-cycle assessment. We compare more than 60 case studies capturing CO2 from various sources in 5 global regions using different technologies. The platform simultaneously informs various stakeholders about the cost-effectiveness of technologies, process configurations and locations, reveals the molecular characteristics of the top-performing sorbents, and provides insights on environmental impacts, co-benefits and trade-offs. By uniting stakeholders at an early research stage, PrISMa accelerates carbon-capture technology development during this critical period as we aim for a net-zero world.
RESUMO
Analysis of cerebrospinal fluid (CSF), including lactate, is key for diagnosis of acute meningitis. Since blood gas analyzers (BGA) enable rapid and safe blood-lactate measurements, we evaluated the reliability of RAPIDPoint 500 BGA to provide a fast and accurate measure of CSF lactate. In this study, CSF lactate levels were measured by a reference assay and on RAPIDPoint 500 BGA. Comparability was evaluated through difference analysis, using Bland Altman test, and linear regression analysis, using the Passing Bablok test. Agreement rate according to CSF lactate (≥3.5 and <3.5 mmol/L) was calculated using kappa (κ) statistic. Population study included 98 CSF samples. Concerning difference analysis, according to Bland-Altman test, bias was 0.13 mmol/L (CI 95%: -0.26 to 0.52 mmol/L. In regression analysis, according to Passing-Bablok equation a systematic difference between both assays was found. In concordance analysis, the interrate realibility was very high (κ: 0.964). According to our resuls, although a systematic difference was detected when lactate levels were measured on RAPIDPoint 500 BGA, the results from Bland-Altman test and the high agreement rate support that this POCT analyzer could be useful for a early and safe detection of patients with high probability of increased CSF lactate level.
Assuntos
Ácido Láctico , Testes Imediatos , Humanos , Reprodutibilidade dos Testes , Gasometria , ViésRESUMO
BACKGROUND: Changes in health needs led to an increase in virtual care practices such as telemedicine. Nursing plays an essential role in this practice as it is the key to accessing the healthcare system. It is important that this branch of nursing is developed considering all the ethical aspects of nursing care, and not just the legal concepts of the practice. However, this question has not been widely explored in the literature and it is of crucial relevance in the new concept of care. OBJECTIVE: The purpose of this scoping review is to identify the ethical aspects of the development of telemedicine from a nursing practice perspective. METHODS: A scoping review of the literature based on Arksey and O'Malley's framework. The search was conducted in Scopus, PubMed/MEDLINE and CINAHL databases, from 2012 to 2022. A total of 1322 articles were retrieved, of which 12 met the inclusion criteria. ETHICAL CONSIDERATIONS: The research was conducted in accordance with the best scientific practices. FINDINGS: The most relevant aspects were the safety of the patient, the benefits for the user and the digital competence of the professionals. Informed consent and patient's willingness to use new technologies were relevant to the practice, as was person-centered care and how telemedicine can influence the quality of the therapeutic relationship. Another relevant issue was the concern about professional competence for optimal outcomes. CONCLUSION: It is necessary to further explore and develop the ethical aspects of the new practices, disassociating them from the legal aspects only. Professionals demand more training providing them with more competence and confidence.
Assuntos
Telemedicina , Humanos , Telemedicina/ética , Ética em Enfermagem , Enfermeiras e Enfermeiros/psicologia , Enfermeiras e Enfermeiros/estatística & dados numéricos , Atitude do Pessoal de SaúdeRESUMO
INTRODUCTION: Cancer patients are more susceptible to infections, and infection can be more severe than in patients without cancer diagnosis. We conducted this retrospective study in patients admitted for SARS-CoV-2 infection in order to find differences in inflammatory markers and mortality in cancer patients compared to others. METHODS: We reviewed the electronic records of patients admitted for SARS-CoV-2 infection confirmed by PCR from March to September 2020. Data on socio-demographics, comorbidities, inflammatory makers, and cancer-related features were analyzed. RESULTS: 2,772 patients were admitted for SARS-CoV-2, to the Hospital Universitario Ramón y Cajal in Madrid during this period. Of these, 2,527 (91%) had no history of neoplastic disease, 164 (5.9%) patients had a prior history of cancer but were not undergoing oncological treatment at the time of infection, and 81 (2.9%) were in active treatment. Mortality in patients without a history of cancer was 19.5%, 28.6% for patients with a prior history of cancer, and 34% in patients with active cancer treatment. Patients in active oncology treatment with the highest mortality rate were those diagnosed with lung cancer (OR 5.6 95% CI: 2.2-14.1). In the multivariate study, active oncological treatment (OR 2.259 95% CI: 1.35-3.77) and chemotherapy treatment (OR 3.624 95% CI: 1.17-11.17), were statistically significant factors for the risk of death for the whole group and for the group with active oncological treatment, respectively. CONCLUSION: Cancer patients on active systemic treatment have an increased risk of mortality after SARS-CoV-2 infection, especially with lung cancer or chemotherapy treatment.
Assuntos
COVID-19 , Neoplasias Pulmonares , Humanos , COVID-19/epidemiologia , Oncologia , Estudos Retrospectivos , SARS-CoV-2RESUMO
The doping of atomic clusters with transition-metal atoms modifies to a lesser or greater extent the catalytic properties of the pure forms. Here we study by means of density functional theory (DFT) the adsorption of up to six NO molecules on Au10- and Au9Zn- clusters, both with well-tested D3h planar geometry, to learn how precise modifications of the atomic and electronic environment, namely one atom and a valence electron, affect the bonding of multiple NO molecules to anionic gold clusters. First, we confirm that these clusters have D3h symmetry as determined by L. S. Wang and coworkers using photoelectron spectroscopy experiments [Kulichenko et al., J. Phys. Chem. A, 2021, 125, 4606]. Second, we verify that Au10(NO)n- with n ≤ 6 does not form adsorbed (NO)2 dimers, as realized by the experiments of Ma and coworkers [Ma et al., Phys. Chem. Chem. Phys., 2020, 22, 25227] using a mini flow-tube reactor at 150 K. Third, we discover that the ground state of the doped Au9Zn(NO)6- compound forms a (NO)2cis-dimer bridging two non-corner Au atoms of the Au9Zn(NO)4- compound. The discussion of adsorption energies, spin multiplicities, bond lengths, charge trends, vibrational strength frequencies of adsorbed NO's, and projected density of states (PDOS), brings additional testable differences between Au10(NO)n- and Au9Zn(NO)n- compounds (n ≤ 6).
RESUMO
Climate change and exposure to environmental pollutants play a key role in the onset and aggravation of allergic diseases. As different climate-dependent patterns of molecular immunoglobulin E (IgE) reactivity have been regionally described, we sought to investigate the evolving allergen exposome in distinctive allergic phenotypes and subtropical weather conditions through a Precision Allergy Molecular Diagnosis (PAMD@) model. Concurrent sensitization to several house dust mites (HDM) and storage mite molecules were broadly dominant in the investigated cohort, followed by the major cat allergen Fel d 1, and regardless of the basal allergic disease. Although a complex repertoire of allergens was recognized, a steadily increasing number of IgE binding molecules was associated with the complexity of the underlying atopic disease. Besides the highly prevalent IgE responses to major HDM allergens, Der p 21, Der p 5, and Der p 7 also showed up as serodominant molecules, especially in subjects bothered by asthma and atopic dermatitis. The accurate characterization of the external exposome at the molecular level and their putative role as clinically relevant allergens is essential to elucidate the phenotypic diversity of atopic disease in terms of personalized diagnosis and therapy.
Assuntos
Dermatite Atópica , Expossoma , Hipersensibilidade , Humanos , Alérgenos , Dermatite Atópica/diagnóstico , Fenótipo , Imunoglobulina E , Antígenos de DermatophagoidesRESUMO
In this work, we have studied, within density functional theory, the interaction of NO with pure and oxidized silver clusters, both anionic and cationic, composed from 11 to 13 Ag atoms. In that size interval, shell closing effects are not expected, and structural and electronic odd-even effects will determine the strength of interaction. First, we obtained that species Agn ± and AgnO± with odd number of electrons (n = 12) adsorb NO with higher energy than their neighbors (n = 11 and 13). This result is in agreement with the facts observed in recent mass spectroscopy measurements, which were performed, however, at finite temperature. The adsorption energy is about twice for oxidized clusters compared to pure ones and higher for anions than for cations. Second, the adsorption of another NO molecule on AgnNO± forms Agn(NO)2 ±, with the dimer (NO)2 in cis configuration, and binding the two N atoms with two neighbor Ag atoms. The n = 12 species show the higher adsorption energy again. Third, in the absence of reaction barriers, all complexes Agn(NO)2 ± dissociate spontaneously into AgnO± and N2O, except the n = 12 anion. The maximum high barrier along the dissociation path of Ag13(NO)2 - is about 0.7 eV. Further analysis of projected density of states for Ag11-13(NO)x ± (x = 0, 1, 2) molecules shows that bonding between NO and Ag clusters mainly occurs in the energy range between -3.0 and 3.0 eV. The overlap between 4d of Ag and 2p of N and O is larger for Ag12(NO)2 ± than for neighbor sizes. For n = 12, the d bands are close to the (NO)2 2π orbital, leading to extra back-donation charge from the 4d of Ag to the closer 2π orbital of (NO)2.
RESUMO
BACKGROUND: Family Presence During Invasive Procedures (FPDI) generates controversy among healthcare professionals. Twibell and her team designed an instrument that measured nurses' Risk-Benefit and Self-Confidence perceptions regarding family presence during resuscitation and was used in numerous studies. OBJECTIVES: Evaluate the new tool for Family Presence Risk-Benefit and Family Presence Self-Confidence during invasive procedures and find out the opinions of the medical and nursing staff on FPDIP. METHOD: Cross-sectional methodological pilot study. Online and paper questionnaires modified from a previous translation. A factor analysis was performed for the validity of the indices and bivariate analysis for all the variables. Ethical approvals and research permissions were obtained according to national standards. RESULTS: One hundred twenty healthcare professionals (22.18%) answered the survey. Cronbach's α on the Family Presence Risk-Benefit scale was 0.877. Cronbach's α on the Family Presence Self-Confidence scale was 0.937. The correlation between the Risk-Benefit and Self-confidence variables is significant and with a moderate intensity of the relationship. A lower predisposition to Family Presence During Invasive Procedures is observed. Physicians are more reluctant than nurses. CONCLUSIONS: The FPDI generates controversy as it alters health professionals' routines when they decide whether to allow it or not. There is a tendency for younger professionals to support FPDI. In general, health professionals, mainly physicians, do not favor FPDI. Health workers who perceive fewer risks and more benefits in FPDI and have greater self-confidence are more in favor of FPDI. The psychometric properties and internal consistency of the questionnaire indicate the validity and reliability of this tool.
Assuntos
Atitude do Pessoal de Saúde , Família , Humanos , Feminino , Projetos Piloto , Estudos Transversais , Reprodutibilidade dos Testes , Inquéritos e Questionários , PsicometriaRESUMO
PURPOSE: To characterize the clinical features and outcomes of pediatric patients with retropharyngeal (RPA) or parapharyngeal abscesses (PPA) managed only with medical treatment and showing the importance of early symptoms and imaging studies in the diagnosis of deep neck space infections (DNIs) in children. METHODS: A retrospective analysis of all patients diagnosed with RPA and PPA between 2007 and 2017 was performed in Hospital Universitario Central de Asturias. RESULTS: 30 children were identified, with 11 RPA and 19 PPA. 23 children (76.7%) were under 5 years old, and all were treated with intravenous amoxicillin/clavulanic acid and corticosteroids. Torticollis and fever were present in all patients. The mean length of hospital stay was 7.5 days. There were no complications associated. CONCLUSION: DNIs can be treated in a conservative way, reserving the surgical drainage for cases with a complication associated (airway compromise, lack of response to antibiotic therapy, immunocompromised patients). Treatment with intravenous antibiotics and corticosteroids is a safe option, reducing the duration of symptoms and the length of hospital stay.
Assuntos
Doenças Faríngeas , Abscesso Retrofaríngeo , Corticosteroides/uso terapêutico , Combinação Amoxicilina e Clavulanato de Potássio/uso terapêutico , Antibacterianos/uso terapêutico , Criança , Pré-Escolar , Tratamento Conservador , Drenagem/métodos , Humanos , Pescoço , Doenças Faríngeas/diagnóstico por imagem , Doenças Faríngeas/tratamento farmacológico , Abscesso Retrofaríngeo/diagnóstico por imagem , Abscesso Retrofaríngeo/tratamento farmacológico , Estudos Retrospectivos , Esteroides/uso terapêuticoRESUMO
Brain mitochondrial function is critical for numerous neuronal processes. We recently identified a link between brain energy and social dominance, where higher levels of mitochondrial function resulted in increased social competitive ability. The underlying mechanism of this link, however, remains unclear. Here, we investigated the contribution of astrocytic release of adenosine triphosphate (ATP) through the type 2 inositol 1,4,5-triphosphate receptor to social dominance behavior. Mice lacking the type 2 inositol 1,4,5-triphosphate receptor were characterized for their social dominance behavior, as well as their performance on a nonsocial task, the Morris Water Maze. In parallel, we also examined mitochondrial function in the medial prefrontal cortex, nucleus accumbens, and hippocampus to investigate how deficiencies in astrocytic ATP could modulate overall mitochondrial function. While knockout mice showed similar competitive ability compared with their wild-type littermates, dominant knockout mice exhibited a significant delay in exerting their dominance during the initial encounter. Otherwise, there were no differences in anxiety and exploratory traits, spatial learning and memory, or brain mitochondrial function in either light or dark circadian phases. Our findings point to a marginal role of astrocytic ATP through IP3 R2 in social competition, suggesting that, under basal conditions, the neuronal compartment is predominant for social dominance exertion.
Assuntos
Sinalização do Cálcio , Cálcio , Trifosfato de Adenosina/metabolismo , Animais , Cálcio/metabolismo , Inositol , Receptores de Inositol 1,4,5-Trifosfato/genética , Receptores de Inositol 1,4,5-Trifosfato/metabolismo , Camundongos , Camundongos Knockout , Predomínio SocialRESUMO
Few effective therapies exist for acute myeloid leukaemia (AML), in part due to the molecular heterogeneity of this disease. We sought to identify genes crucial to deregulated AML signal transduction pathways which, if inhibited, could effectively eradicate leukaemia stem cells. Due to difficulties in screening primary cells, most previous studies have performed next-generation sequencing (NGS) library knockdown screens in cell lines. Using carefully considered methods including evaluation at multiple timepoints to ensure equitable gene knockdown, we employed a large NGS short hairpin RNA (shRNA) knockdown screen of nearly 5 000 genes in primary AML cells from six patients to identify genes that are crucial for leukaemic survival. Across various levels of stringency, genome-wide bioinformatic analysis identified a gene in the NOX family, NOX1, to have the most consistent knockdown effectiveness in primary cells (P = 5â39 × 10-5 , Bonferroni-adjusted), impacting leukaemia cell survival as the top-ranked gene for two of the six AML patients and also showing high effectiveness in three of the other four patients. Further investigation of this pathway highlighted NOX2 as the member of the NOX family with clear knockdown efficacy. We conclude that genes in the NOX family are enticing candidates for therapeutic development in AML.
Assuntos
Leucemia Mieloide Aguda/genética , Descoberta de Drogas , Regulação Leucêmica da Expressão Gênica , Técnicas de Silenciamento de Genes , Terapia Genética , Genômica , Sequenciamento de Nucleotídeos em Larga Escala , Humanos , Leucemia Mieloide Aguda/terapia , Terapia de Alvo Molecular , NADPH Oxidase 2/genéticaRESUMO
OBJECTIVES: Several studies have described peach tree (PT) as an occupational allergen. The aim of this work was to assess the effect of Prunus persica 9 (Pru p 9), a recently identified allergen from PT pollen, in exposed workers. METHODS: The study included people who reported respiratory symptoms after handling PT in orchards during the flowering period (Blanca village, Murcia region, south-east Spain). After completing a detailed questionnaire, participants underwent skin prick test (SPT) and nasal provocation test (NPT). The IgE response was analysed by SDS-PAGE and immunoblotting assays. RESULTS: A total of 21 cases were included (mean age 45 years; 57% women). Most were polysensitised to common pollens, although one person was sensitised only to PT pollen. All cases had a positive SPT to this pollen, and 43% also to Pru p 9. All participants reported having rhinitis, and six participants reported having also asthma. Immunoblotting showed a heterogeneous IgE pattern for several proteins, with Pru p 9 recognised in nine cases. Most participants sensitised to PT pollen and Pru p 9 had positive NPTs, while those who were not sensitised to Pru p 9 tested negative. CONCLUSIONS: We demonstrate for the first time that Pru p 9, an allergen from PT pollen, can induce respiratory symptoms following occupational exposure. This must be considered a relevant allergen when people working with PT cultivars develop respiratory symptoms.
Assuntos
Doenças dos Trabalhadores Agrícolas/imunologia , Asma Ocupacional/imunologia , Exposição Ocupacional/efeitos adversos , Pólen/imunologia , Prunus persica/imunologia , Rinite Alérgica Sazonal/imunologia , Testes de Provocação Brônquica , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Testes Cutâneos , EspanhaRESUMO
BACKGROUND: Family Presence during Cardiopulmonary Resuscitation has been studied both to identify the opinions of health professionals, patients, and family members, and to identify benefits and barriers, as well as to design protocols for its implementation. R. Twibell and her team designed an instrument that measured nurses' perceptions of Risks-Benefits and Self-Confidence regarding Family Presence during Resuscitation. There are few studies in Spain on this practice. METHODS: The aim is to adapt and validate into Spanish the Family Presence Risk-Benefit scale and Family Presence Self-Confidence scale instrument. For this purpose, this instrument was translated cross-culturally, and administered in paper and online version. Statistical tests were carried out for the validity of the questionnaire. Five hundred forty-one healthcare professionals were invited to respond. The results were analyzed by the same statistical procedures as in the original scale. Ethical approvals and research permissions were obtained according to national standards. RESULTS: Two hundred thirty-seven healthcare professionals (43.8%) answered the survey (69% women), of whom 167 were nurses. Validation of instruments: Cronbach's α in Family Presence Risk-Benefit scale was 0.94. Cronbach's α in Family Presence Self-Confidence scale was 0.96. Factor Analysis Kaiser, Meyer and Olkin (KMO) was greater than 0.9. The correlation between the two measured scales, is significant and has a moderate intensity of the relationship (r = 0.65 and α < 0.001). A lower predisposition to Family Presence during Cardiopulmonary Resuscitation is observed, but the pure detractors are only 12%. Doctors are more reluctant than nurses. CONCLUSIONS: The psychometric properties of the questionnaire in Spanish indicate high validity and reliability. Risk-Benefit perception and Self-Confidence are related to the healthcare professionals who consider the Family Presence to be beneficial. More studies in different contexts are necessary to confirm the psychometric results and validity of this instrument in Spanish.
Assuntos
Atitude do Pessoal de Saúde , Família , Feminino , Humanos , Masculino , Psicometria , Reprodutibilidade dos Testes , Espanha , Inquéritos e QuestionáriosRESUMO
BACKGROUND: Family presence during invasive procedures and cardiopulmonary resuscitation (FPDR) is a highly controversial issue, with divergence of opinion among health professionals, with clinical evidence in favor, and with barriers to its implementation in comprehensive patient care. Many international organizations support health policies for its implementation, but it is not a widespread practice. Little research has been conducted on this subject from the perspective of patients and families. OBJECTIVE: To learn opinions, perceptions, and desires of family members and patients in terms of family presence during invasive procedures and cardiopulmonary resuscitation. METHOD: Qualitative descriptive study, using semi-structured interviews with relatives and patients regarding their experiences and perceptions about FPDR (n = 18) from 8 October 2017 to 8 March 2018. The interviews were recorded and transcribed verbatim for later analysis using the method of content analysis. ETHICAL CONSIDERATIONS: This study has the approval of the Clinical Research Ethics Committee of the Fundació Unió Catalana d'Hospitals and ethical considerations were carefully regarded throughout the study. RESULTS: Three significant categories were identified: knowledge, respect for rights, and accompaniment of the patient, relating FPDR to courage, emotional support, and trust in professionals. CONCLUSION: FPDR is an unusual practice; it is not offered to patients or their families, and it is not considered a patient's right, although most of the interviewees support it. The desire for accompaniment is conditioned by the courage and knowledge of the accompanying persons, as well as the degree of invasiveness of the procedures. The results of this study provide information for a change of vision in patient-centered care.
Assuntos
Reanimação Cardiopulmonar , Visitas a Pacientes , Atitude do Pessoal de Saúde , Família , Humanos , Relações Profissional-Família , RessuscitaçãoRESUMO
OBJECTIVES: To characterize amikacin population pharmacokinetics in patients with hypoalbuminaemia and to develop a model-based interactive application for amikacin initial dosage. METHODS: A population pharmacokinetic model was developed using a non-linear mixed-effects modelling approach (NONMEM) with amikacin concentration-time data collected from clinical practice (75% hypoalbuminaemic patients). Goodness-of-fit plots, minimum objective function value, prediction-corrected visual predictive check, bootstrapping, precision and bias of parameter estimates were used for model evaluation. An interactive model-based simulation tool was developed in R (Shiny and R Markdown). Cmax/MIC ratio, time above MIC and AUC/MIC were used for optimizing amikacin initial dose recommendation. Probabilities of reaching targets were calculated for the dosage proposed. RESULTS: A one-compartment model with first-order linear elimination best described the 873 amikacin plasma concentrations available from 294 subjects (model development and external validation groups). Estimated amikacin population pharmacokinetic parameters were CL (L/h) = 0.525â+â4.78 × (CKD-EPI/98) × (0.77 × vancomycin) and V (L) = 26.3 × (albumin/2.9)-0.51 × [1â+â0.006 × (weight - 70)], where CKD-EPI is calculated with the Chronic Kidney Disease Epidemiology Collaboration equation. AMKdose is a useful interactive model-based application for a priori optimization of amikacin dosage, using individual patient and microbiological information together with predefined pharmacokinetic/pharmacodynamic (PKPD) targets. CONCLUSIONS: Serum albumin, total bodyweight, estimated glomerular filtration rate (using the CKD-EPI equation) and co-medication with vancomycin showed a significant impact on amikacin pharmacokinetics. A powerful interactive initial dose-finding tool has been developed and is freely available online. AMKdose could be useful for guiding initial amikacin dose selection before any individual pharmacokinetic information is available.
Assuntos
Amicacina , Hipoalbuminemia , Antibacterianos , Taxa de Filtração Glomerular , Humanos , Modelos Biológicos , VancomicinaRESUMO
Proteases are ideal target biomarkers as they have been implicated in many disease states, including steps associated with cancer progression. Electrochemical peptide-based biosensors have attracted much interest in recent years. However, the significantly large size of the electrodes typically used in most of these platforms has led to performance limitations. These could be addressed by the enhancements offered by microelectrodes, such as rapid response times, improved mass transport, higher signal-to-noise and sensitivity, as well as more localised and less invasive measurements. We present the production and characterisation of a miniaturised electrochemical biosensor for the detection of trypsin, based on 25 µm diameter Pt microelectrodes (rather than the ubiquitous Au electrodes), benchmarked by establishing the equivalent Pt macroelectrode response in terms of quantitative response to the protease, the kinetics of cleavage and the effects of non-specific protein binding and temperature. Interestingly, although there was little difference between Au and Pt macroelectrode response, significant differences were observed between the responses of the Pt macroelectrode and microelectrode systems indicative of increased reproducibility in the microelectrode SAM structure and sensor performance between the electrodes, increased storage stability and a decrease in the cleavage rate at functionalised microelectrodes, which is mitigated by measurement at normal body temperature. Together, these results demonstrate the robustness and sensitivity of the miniaturised sensing platform and its ability to operate within the clinically-relevant concentration ranges of proteases in normal and disease states. These are critical features for its translation into implantable devices.
Assuntos
Técnicas Biossensoriais/métodos , Peptídeos/metabolismo , Platina/química , Tripsina/análise , Técnicas Biossensoriais/instrumentação , Técnicas Eletroquímicas , Cinética , Microeletrodos , Miniaturização , Peptídeos/química , Temperatura , Tripsina/metabolismoRESUMO
We consider the different structures that a magnetic nanowire adsorbed on a surface may adopt under the influence of external magnetic or electric fields. First, we propose a theoretical framework based on an Ising-like extension of the 1D Frenkel-Kontorova model, which is analyzed in detail using the transfer matrix formalism, determining a rich phase diagram displaying structural reconstructions at finite fields and an antiferromagnetic-paramagnetic phase transition of second order. Our conclusions are validated using ab initio calculations with density functional theory, paving the way for the search of actual materials where this complex phenomenon can be observed in the laboratory.
RESUMO
Anthropogenic CO2 is the main contributor to the increased concentration of greenhouse gases in the atmosphere, and thus utilising waste CO2 for the production of valuable chemicals is a very appealing strategy for reducing CO2 emissions. The catalytic fixation of CO2 with epoxides for the production of cyclic carbonates has gained increasing attention from the research community in search of an alternative to the homogeneous catalytic routes, which are currently being used in industry. A novel photocatalytic heterogeneous approach to generate cyclic carbonates is demonstrated in this work. Hyper-branched microstructured Ru modified TiO2 nanorods decorated with RuO2 nanoparticles, supported on fluorine-doped tin oxide (FTO) glass were fabricated for the first time and were used to catalyse the photo-generation of propylene carbonates from propylene oxides. Propylene carbonate was used as a reference for cyclic carbonates. The photo-generation of cyclic carbonates from epoxides and CO2 was carried out at a maximum temperature of 55 °C at 200 kPa in a stainless steel photoreactor with a quartz window, under solar irradiation for 6 h. The best performing photocatalyst exhibited an estimated selectivity of 83% towards propylene carbonates under the irradiation of a solar simulator.
RESUMO
We have studied the adsorption and coadsorption properties of one or more X = Ar, N2, O2, and NO adsorbates on cationic silver clusters Ag11-13+, whose sizes are in the open shell region of metal clusters, aiming to understand the observed odd-even effects in the abundance spectra of Ag11-13+·mX complexes. All calculations were performed self-consistently using a non-local van der Waals correlation functional, covering the different nature of the interactions between the silver substrate and the several adsorbates, which range from dispersion (London) forces for Ar, non covalent π-π interactions for N2, charge-transfer interactions for O2 and NO, and the covalent Ag-Ag bond in the nude silver cluster. Despite the wide interval of adsorption energies, spanning two orders of magnitude, we have been able to explain the following experimental facts. For X = Ar, N2, and O2 reactions with Ag11-13+, it was observed in the mass spectra an abundance peak at n = 12 [M. Schmidt, et al., ChemPhysChem, 2015, 16, 855]. In addition it was observed the competitive adsorption of two or more N2 molecules, and the cooperative effect of adsorbing N2 together with O2 molecules. For X = NO, an abundance peak at n = 12 has been also observed [J. Ma, et al., Phys. Chem. Chem. Phys., 2016, 18, 12819]. We find that the main factors determining these properties are the different core motifs of the cluster geometry (pentagonal bipiramid for Ag11+ and Ag13+, but triangular prism for Ag12+) and, on the other hand, the odd number of valence electrons for Ag12+, leading to a smaller HOMO-LUMO gap than those of its neighbours. Further details about the preferred adsorption sites, dipole moments, and dipole polarizabilities are also discussed.