44 research outputs found
Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate
Reductive Small Molecule Transformations with Pyrazolate-Based Bimetallic Complexes
The activation of small molecules (NO, O2, CO, CO2, N2, etc.) is important in a multitude of fields such as biology, medicine and industrial catalysis. Many synthetic catalysts were inspired by the active sites of metalloenzymes, where the synergy between metals can be beneficial for small molecule activation. A series of new complexes supported by a pyrazolate bridged bis-β-diketiminate ligand scaffolds were synthesized to combine the efficiency of the nacnac framework with the cooperativity of bimetallic systems for small molecule activation.
The focus is initially dedicated to the activation of N2 in relation to the redox chemistry of a dinickel(II) dihydride complex and a dinickel(I) complex. The reactivity towards CO of a dinickel(II) complex which features an intramolecular Ni–C bond and agostic interactions and of a dinickel(II) μ-OH complex is subsequently investigated.2025-01-3
Role of the Cysteine in R3 Tau Peptide in Copper Binding and Reactivity
Tau is a widespread neuroprotein that regulates the cytoskeleton assembly. In some neurological disorders, known as tauopathies, tau is dissociated from the microtubule and forms insoluble neurofibrillary tangles. Tau comprises four pseudorepeats (R1–R4), containing one (R1, R2, R4) or two (R3) histidines, that potentially act as metal binding sites. Moreover, Cys291 and Cys322 in R2 and R3, respectively, might have an important role in protein aggregation, through possible disulfide bond formation, and/or affecting the binding and reactivity of redox-active metal ions, as copper. We, therefore, compare the interaction of copper with octadeca-R3-peptide (R3C) and with the mutant containing an alanine residue (R3A) to assess the role of thiol group. Spectrophotometric titrations allow to calculate the formation constant of the copper(I) complexes, showing a remarkable stronger interaction in the case of R3C (log Kf = 13.4 and 10.5 for copper(I)-R3C and copper(I)-R3A, respectively). We also evaluate the oxidative reactivity associated to these copper complexes in the presence of dopamine and ascorbate. Both R3A and R3C peptides increase the capability of copper to oxidize catechols, but copper-R3C displays a peculiar mechanism due to the presence of cysteine. HPLC-MS analysis shows that cysteine can form disulfide bonds and dopamine-Cys covalent adducts, with potential implication in tau aggregation process
Hexanuclear Copper(I) Hydride from the Reduction-Induced Decarboxylation of a Dicopper(II) Formate
Crime Writing and Social Marketing as Creative Work
Crime fiction has become one of Sweden's biggest cultural exports. In this chapter, we discuss how individual crime fiction writers are used as role models for how creative industries should function in both local and global contexts. They appear to be at the forefront of outreach to an international audience, how to market books and your own author brand through events, and how to make a successful living from your writing. There is a higher demand for personal exposure of writers in the public sphere that can almost overshadow the interest shown in their work. The aim of this chapter is to understand the conditions and limitations that crime fiction writers face in the contemporary Swedish crime book market. We will do this by focusing on some writers’ experiences of working in the business of crime writing. The connections and/or tensions between building a professional identity as a crime writer and the writer's personal lifestyle are in focus. In this context, we address the issue of social marketing through digital media, and we have chosen to look more closely into some individual writers and their personal experiences
Growth, History, or Institutions? What Explains State Fragility in Sub-Saharan Africa
We explore the determinants of state fragility in sub-Saharan Africa. Controlling for a wide range of economic, demographic, geographic and istitutional regressors, we find that institutions, and in particular the civil liberties index and the number of revolutions, are the main determinants of fragility, even taking into account their potential endogeneity. Economic factors such as income growth and investment display a non robust impact after controlling for omitted variables and reverse causality. Colonial variables reflecting the history of the region display a marginal impact on fragility once institutions are accounted for.State fragility, Africa, institutions, colonial history.
Ideological evolution and feminist writing in the Tsunamis (Mexico and Spain)
En el año 2018, la autora mexicana Gabriela Jáuregui coordinó un conjunto de ensayos bajo el título de Tsunami, en el que participaron voces fundamentales de las letras mexicanas como Yásnaya Elena A. Gil, Margo Glantz, Cristina Rivera Garza, Vivian Abenshushan o Verónica Gerber Bicecci. Un año después, Marta Sanz coordinó la versión española de este Tsunami, con la participación de autoras como Cristina Fallarás, Sara Mesa, Cristina Morales o Laura Freixas. En este texto nos preguntaremos cuáles son los caminos de ida y vuelta de los feminismos entre España y México. Haremos hincapié en la importancia fundamental que han tenido los feminismos latinoamericanos en la configuración del panorama feminista español y ahondaremos en la idea de que la lucha feminista no puede considerarse solo a nivel nacional, sino que hay un flujo de olas, un devenir ideológico sin el cual no habría sido posible alcanzar la lucha articulada que venimos presenciando en los últimos años.In 2018, Mexican author Gabriela Jáuregui coordinated a book under the title Tsunami, with the participation of fundamental voices of Mexican letters such as Yásnaya Elena A. Gil, Margo Glantz, Cristina Rivera Garza, Vivian Abenshushan or Verónica Gerber Bicecci. A year later, Marta Sanz coordinated the Spanish version of this Tsunami, with the participation of authors such as Cristina Fallarás, Sara Mesa, Cristina Morales or Laura Freixas. In this text we will ask ourselves which are the influences of feminisms between Spain and Mexico. We will emphasize the fundamental importance that Latin American feminisms have had in the configuration of the Spanish feminist panorama and we will delve into the idea that the feminist struggle cannot be considered only at a national level, but that there is a flow of waves, an ideological evolution without which it would not have been possible to achieve the articulated struggle that we have been witnessing in recent years.En el año 2018, la autora mexicana Gabriela Jáuregui coordinó un conjunto de ensayos bajo el título de Tsunami, en el que participaron voces fundamentales de las letras mexicanas como Yásnaya Elena A. Gil, Margo Glantz, Cristina Rivera Garza, Vivian Abenshushan o Verónica Gerber Bicecci. Un año después, Marta Sanz coordinó la versión española de este Tsunami, con la participación de autoras como Cristina Fallarás, Sara Mesa, Cristina Morales o Laura Freixas. En este texto nos preguntaremos cuáles son los caminos de ida y vuelta de los feminismos entre España y México. Haremos hincapié en la importancia fundamental que han tenido los feminismos latinoamericanos en la configuración del panorama feminista español y ahondaremos en la idea de que la lucha feminista no puede considerarse solo a nivel nacional, sino que hay un flujo de olas, un devenir ideológico sin el cual no habría sido posible alcanzar la lucha articulada que venimos presenciando en los últimos años
Firm innovations from voluntary dyadic engagement with nonprofit organisations: an exploratory UK study
This dissertation presents the findings of an exploratory collective case-study examining
corporate innovations arising from voluntary dyadic engagement between UK firms and
nonprofit organisations (NPOs) focused on social issues.
Whilst the extant literature demonstrates that pro-active engagement with NPOs can
assist firms innovate, there has been no empirical work which explores the relationship
between the engagement and the innovation outcome: a gap which this research
addresses. In doing so, it illustrates how concepts and constructs from the innovation
management literature can be applied usefully to the stakeholder and cross-sector
collaboration field. To date, empirical studies addressing firm-NPO engagements have
concentrated overwhelmingly on partnerships to address environmental issues. This
study provides insights into cross-sector engagements focused on addressing social
issues.
Using a form of analytic induction to evaluate qualitative case-data from ten dyadic
engagements, this dissertation addresses the question: “how do firms innovate through
engagement with social issues nonprofit organisations?” The research found that
product and service innovations resulted from engagements where the firm had an
external stakeholder orientation and was focused on delivering tangible demonstrations
of corporate responsibility. Process innovations, by contrast, were produced from
engagements where firms had an internal stakeholder orientation. Two distinctions
were noted in the innovation process, too. Firstly, a more exploratory approach to
dyadic engagement activities, which resulted in an emergent innovation process; and
secondly, a focused and pre-determined search activity to exploit the resources of the
nonprofit partner which demonstrated a more planned innovation process. In addition,
two distinct boundary spanning roles were identified: in dyads with no direct
management involvement in the engagement, the role was associated with formal
responsibilities from senior management to „manage‟ innovation opportunities and
outcomes. In dyads where senior management were involved, there was no such
formality; the boundary spanner acted to „facilitate‟ search and exploration to locate
opportunities for innovation through idea exchange.
The application of innovation constructs to the business and society field has enabled
firm engagement with nonprofit stakeholders to be examined through a new lens and
demonstrated how firms innovate from such relationships. In particular it has
highlighted the key role played by the firm boundary spanner (relationship manager)
and how this role alters depending on senior management involvement: a distinction
which has not been made in the extant literature and would benefit from further
examination
Author correction: Study of 300,486 individuals identifies 148 independent genetic loci influencing general cognitive function
Christina M. Lill, who contributed to analysis of data, was inadvertently omitted from the author list in the originally published version of this article. This has now been corrected in both the PDF and HTML versions of the article
The mediating role of epigenetic ageing in the nonlinear association between body mass index and survival : a prospective cohort analysis of the US Health and Retirement Study
Background: The role of biological ageing in the association between body mass index (BMI) and survival remains unclear. We examined whether epigenetic age acceleration (EAA), a biomarker of biological ageing, mediates the BMI-survival association. Methods: We analysed data from 3840 participants (aged 51–100) in the 2016 US Health and Retirement Study, with survival information through 2020. Mediation analyses were performed using linear regression and Gompertz proportional hazards models with restricted cubic splines, adjusting for age, sex, ethnicity/race, smoking, education, and metabolic health. Average direct effects (ADE) of BMI and average causal mediation effects of EAA (HannumAgeAcc, PhenoAgeAcc, GrimAgeAcc, and DunedinPace) on survival time were estimated with 95% confidence intervals (CI). Findings: Associations between BMI, EAA, and survival were nonlinear: high and low BMIs were associated with higher EAA and reduced survival time. ADEs of high BMI (35 kg/m2 versus 27 kg/m2) were not statistically significant (reduced survival time: 1.21–1.58 years) but significant for low BMI (19 kg/m2 versus 27 kg/m2, reduced survival time: 5.60–6.38 years). For high BMI, mediation was significant through all EAAs, with reduced survival time ranging from 0.28 to 0.71 years, accounting for 15–37% of total effects. For low BMI, mediation was statistically significant through HannumAgeAcc (reduced survival time: 0.44, CI: 0.08–0.86) and GrimAgeAcc (reduced survival time: 0.73, CI: 0.15–1.38), accounting for 7–11% of total effects. Interpretation: EAA partially mediated the high BMI-survival association, supporting the mediating role of accelerated ageing in the obesity-survival relationship. Mediation through EAA in the low BMI-survival association was weaker, indicating that alternative mechanisms, other than accelerated ageing, may dominate. Funding: Forte, Vetenskaprådet, SFOepi, Karolinska Institutet's Research Foundation, Loo and Hans Osterman Foundation, the Foundation for Geriatric Diseases at Karolinska Institutet. CC BY 4.0© 2025 The Author(s)Correspondence Address: P. Ler; Department of Medical Epidemiology and Biostatistics, Karolinska Institutet, Solna, Nobels väg 12A, 171 65, Sweden; email: [email protected]; I.K. Karlsson; Department of Medical Epidemiology and Biostatistics, Karolinska Institutet, Solna, Nobels väg 12A, 171 65, Sweden; email: [email protected] research was funded by the Swedish Research Council for Health, Working Life and Welfare (Forte; 2022-00672); the Strategic Research Program in Epidemiology (SFOepi) at Karolinska Institutet, Karolinska Institutet’s Research Foundation (2022-01718); Loo and Hans Osterman Foundation (2022-01222, 2023-01855, 2024-02197); the Foundation for Geriatric Diseases at Karolinska Institutet (2022-01296, 2023-01854, 2024-02116); and the Swedish Research Council (Vetenskaprådet; 2016–03081).</p
