Probing the effects of steric bulk on the solution-phase behaviour and redox chemistry of cobalt-diimine complexes

Cobalt-diimine complexes are important structural and redox-active elements in supramolecular assemblies. However, functionalisation of the diimine ligand adjacent to the N-donor atoms can affect dramatically the types of Co-diimine complexes that can form and their redox activity. Herein, we compare the solution phase and redox chemistry of Co(II) complexes with 1,10-phenanthroline, 5,5′-dimethyl-2,2′-bipyridine and 2,9-dimethyl-1,10-phenanthroline (neocuproine). In acetonitrile solutions containing Co(NO3)2 and neocuproine, the dominant species is the mono-diimine complex [Co(neocuproine)(NO3)(CH3CN)2]+. This complex cannot be oxidised, either electrochemically nor with iodine. We rationalise this behaviour by considering the steric constraints placed upon the metal centre by the bulky methyl substituents on the neocuproine ligand. Furthermore, from solutions of [Co(neocuproine)(NO3)(CH3CN)2]+, crystals of formula [Co(neocuproine)2(NO3)]+·[Co(neocuproine)(NO3)3]− can be obtained. We believe that this work will guide the development of Co-diimine supramolecular assemblies by highlighting the extent to which substituents close to the N-donor atoms affect which species form in solution, and their likely redox activity

An empirical examination of the gains in cost-effectiveness from the use of multiple environmental outcome conservation tenders

The production and consumption of environmental goods and services are subject to many of the problems associated with public goods. Due to their non-rival and non-excludable nature, incentives for individuals to invest in their production are often absent. To address this market failure, government agencies have used a number of policy mechanisms to procure the supply of environmental outcomes on behalf of society. Recently, conservation tenders focussing on private land have been a favoured policy instrument used by many government agencies to purchase environmental outcomes in the public interest. The majority of these environmental tenders have focussed on a single environmental outcome. It is contended in this paper that multiple environmental outcomes tenders can be more cost-effective than single outcome tenders as decisions are based on information regarding a wider set of environmental outcomes – a more complete picture. Tenders that focus on more than one outcome capitalise on economies of scope in the production of environmental outcomes, as well as incorporating synergies and trade-offs into decision making. In this paper the results from a synthetic analysis of the benefits derived from running multiple-outcome tenders are compared to single outcome tenders, to empirically estimate potential cost-effectiveness gains. The baseline policy of running a multiple-outcome tender is compared to three alternative policy options: running a single outcome tender, running three single outcome tenders simultaneously, and running three single outcome tenders consecutively. Results indicate that significant cost effectiveness gains can be made by running a multiple-outcome tender compared to the three policy alternatives. These results are analysed, and advantages and limitations of applying multiple-outcome tenders in the field are discussed.Environmental Economics and Policy,

Isolated Voices: Perspectives of Teachers, School Nurses, and Administrators Regarding Implementation of Sexual Health Education Policy.

BackgroundComprehensive sexual health education (SHE) reduces risky sexual behavior and increases protective behavior in adolescents. It is important to understand how professionals responsible for implementing SHE policy interpret state and local policy and what influences their commitment to formal SHE policy implementation.MethodsThis descriptive study explored content and delivery of SHE policy in a rural, southwestern state with high levels of poverty, unintended adolescent pregnancy, and sexually transmitted infections. The social ecological model (SEM) was used to better understand levels of influence on the implementation of SHE policy.ResultsWe conducted telephone surveys with 38 teachers, 63 nurses, and 21 administrators in public secondary schools. There was substantial local variability in the scope and content of SHE curricula. Respondents identified significant barriers to the delivery of SHE content and minimal evaluation of whether educational objectives were met. Based on participant responses, community and organizational SEM levels had the greatest influence on SHE policy implementation, although examples of all SEM levels were identified.ConclusionsGiven perceived challenges regarding subject matter, successful SHE implementation at the local level requires committed stakeholders working in concert at the school and community levels, backed by strong policy commitment at the state level

Knowledge Spillovers from Creation to Exploitation: A Theoretical Model with Implications for Firms and Public Policy

In this paper we present an endogenous growth model in which we investigate the implications of knowledge spillovers between knowledge creators (inventors) and commercializers (innovators). We then turn to the question how such knowledge spillovers affect value creation within and among organizations as well as at the aggregate level and discuss how the internalization of these knowledge spillovers can help improve economic performance at both levels.knowledge spillovers; innovation management; strategic entrepreneurship

ScratchMaths: evaluation report and executive summary

Since 2014, computing has been part of the primary curriculum. ‘Scratch’ is frequently used by schools, and the EEF funded this trial to test whether the platform could be used to improve pupils’ computational thinking skills, and whether this in turn could have a positive impact on Key Stage 2 maths attainment. Good computational thinking skills mean pupils can use problem solving methods that involve expressing problems and their solutions in ways that a computer could execute – for example, recognising patterns. Previous research has shown that pupils with better computational thinking skills do better in maths. The study found a positive impact on computational thinking skills at the end of Year 5 – particularly for pupils who have ever been eligible for free school meals. However, there was no evidence of an impact on Key Stage 2 maths attainment when pupils were tested at the end of Year 6. Many of the schools in the trial did not fully implement ScratchMaths, particularly in Year 6, where teachers expressed concerns about the pressure of Key Stage 2 SATs. But there was no evidence that schools which did implement the programme had better maths results. Schools may be interested in ScratchMaths as an affordable way to cover aspects of the primary computing curriculum in maths lessons without any adverse effect on core maths outcomes. This trial, however, did not provide evidence that ScratchMaths is an effective way to improve maths outcomes

Visfatin reduces gap junction mediated cell-to-cell communication in proximal tubule-derived epithelial cells

Background/Aims: In the current study we examined if the adipocytokine, visfatin, alters connexin-mediated intercellular communication in proximal tubule-derived epithelial cells. Methods: The effects of visfatin (10-200ng/mL) on cell viability and cytotoxicity in HK2-cells were assessed by MTT, crystal violet and lactate dehydrogenase assays. Western blot analysis was used to confirm expression of Cx26, Cx40 and Cx43. The effect of visfatin (10-200ng/mL) on TGF-β1 secretion was confirmed by ELISA, and the effects of both TGF-β1 (2-10ng/mL) and visfatin (10-200ng/mL) on connexin expression were assessed by western blot. Functional intercellular communication was determined using transfer of Lucifer Yellow and paired-whole cell patch clamp electrophysiology. Results: In low glucose (5mM), visfatin (10-200ng/mL) did not affect membrane integrity, cytotoxicity or cell viability at 48hrs, but did evoke a concentration-dependent reduction in Cx26 and Cx43 expression. The expression of Cx40 was unaffected. At 48hrs, visfatin (10-200ng/mL) increased the secretion of TGF-β1 and the visfatin-evoked changes in connexin expression were mimicked by exogenous application of the pro-fibrotic cytokine (2-10ng/ml). Visfatin reduced dye transfer between coupled cells and decreased functional conductance, with levels falling by 63% as compared to control. Although input resistance was increased following visfatin treatment by 166%, the change was not significant as compared to control. The effects of visfatin on Cx-expression and cell-coupling were blocked in the presence of a TGF-β1 specific neutralizing antibody. Conclusions: The adipocytokine visfatin selectively evoked a non-toxic reduction in connexin expression in HK2-cells. The loss in gap-junction associated proteins was mirrored by a loss in functional conductance between coupled cells. Visfatin increased TGF-β secretion and the pattern of change for connexins expression was mimicked by exogenous application of TGF-β1. The effect of visfatin on Cx-expression and dye transfer were negated in the presence of a TGF-β1 neutralising antibody. These data suggest that visfatin reduces connexin-mediated intercellular communication in proximal tubule-derived epithelial cells via a TGF-β dependent pathway. © 2013 S. Karger AG, Base

“Real men don’t hate women”:Twitter rape threats and group identity

On 24th July 2013, feminist campaigner Caroline Criado-Perez's petition to the Bank of England to have Elizabeth Fry's image on the UK's £5 note replaced with the image of another woman was successful. The petition challenged the Bank of England's original plan to replace Fry with Winston Churchill, which would have meant that no woman aside from the Queen would be represented on any UK banknote. Following this, Criado-Perez was subjected to ongoing misogynistic abuse on Twitter, a microblogging social network, including threats of rape and death. This paper investigates this increasingly prominent phenomenon of rape threats made via social networks. Specifically, we investigate the sustained period of abuse directed towards the Twitter account of feminist campaigner and journalist, Caroline Criado-Perez. We then turn our attention to the formation of online discourse communities as they respond to and participate in forms of extreme online misogyny on Twitter. We take a corpus of 76,275 tweets collected during a three month period in which the events occurred (July to September 2013), which comprises 912,901 words. We then employ an interdisciplinary approach to the analysis of language in the context of this social network. Our approach combines quantitative approaches from the fields of corpus linguistics to detect emerging discourse communities, and then qualitative approaches from discourse analysis to analyse how these communities construct their identities

VR Force Feedback Gloves

The goal of this project is to produce a manufacturing plan for a consumer VR glove. The total addressable market of VR is over 170 million global users as of 2022 (Kolmar , 2022) with a serviceable available market of 300,000 users on Meta’s own social platform (Heath, 2022). The targeted Quest 2 platform utilizes handheld controllers, which causes a lack of immersivity in social settings and gaming scenarios. One common use of the platform involves social platforms such as “Horizons” where users meet in a virtual world to interact; handheld controllers don’t allow users to shake hands, make finger gestures, or touch each other’s avatars. Furthermore, users enjoy a breadth of different immersive games from first person shooters to rhythm block slicing games; in this setting, users often interact with physical objects and cannot sense their shape or their mass, nor can they finely interact with simple virtual mechanisms like weapon triggers. At the current time of writing, VR gloves that are readily available for purchase start at $5,000 and can go up to$10,000. However, the previously mentioned 300,000 users of Horizons fall into the consumer market, where accessibility/cost is more constraining; the hardware they use, the Meta Quest 2, costs $400 (Meta, 2022). Thus, these consumer users are unserved by the current market options. This project aims to provide increased immersivity in social and gaming scenarios at a price point that Quest 2 users can afford. Without a thorough customer analysis other than overall sentiment for mass adoption of VR glove technology, this project aims to produce the necessary manufacturing plan and demonstration to appropriately crowd-fund further efforts in offering a product. Deliverables of this project include two prototype demonstrations of the electrical system, mechanical system, and firmware as well as a manufacturing and production plan

An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex

The copper-containing nitrite reductases (CuNIRs) are a class of enzymes that mediate the reduction of nitrite to nitric oxide in biological systems. Metal–ligand complexes that reproduce the salient features of the active site of CuNIRs are therefore of fundamental interest, both for elucidating the possible mode of action of the enzymes and for developing biomimetic catalysts for nitrite reduction. Herein, we describe the synthesis and characterization of a new tris(2-pyridyl) copper complex ([Cu1(NO2)2]) that binds two molecules of nitrite, and displays all three of the common binding modes for NO2−, with one nitrite bound in an asymmetric quasi-bidentate κ2-ONO manner and the other bound in a monodentate fashion with a linkage isomerism between the κ1-ONO and κ1-NO2 binding modes. We use density functional theory to help rationalize the presence of all three of these linkage isomers in one compound, before assessing the redox activity of [Cu1(NO2)2]. These latter studies show that the complex is not a competent nitrite reduction electrocatalyst in non-aqueous solvent, even in the presence of additional proton donors, a finding which may have implications for the design of biomimetic catalysts for nitrite reduction