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Samenvatting In de loop der jaren is een breed aanbod aan eenzaamheidsinterventies voor ouderen ontwikkeld. Het merendeel van de interventies blijkt weinig effectief in het verminderen van eenzaamheid. Om meer inzicht te krijgen in waarom veel interventies niet het gewenste doel bereiken, gaan we in op de werkzame elementen die in interventies worden ingezet om eenzaamheid te reduceren, of waarmee subdoelen bereikt kunnen worden: een sociaal netwerk hebben, erbij horen, intimiteit ervaren, betekenis hebben. Om tot een indeling in werkzame elementen te komen is een kwalitatieve analyse uitgevoerd van 119 eenzaamheidsinterventies, beschreven in 22 reviews van interventies. Het resultaat is een indeling in zeven werkzame elementen: ‘bezigheden’, ‘ontmoeten’, praktisch ondersteunen’, ‘betekenisvol contact’, ‘sociale vaardigheden’, ‘realistische verwachtingen’ en ‘betekenisvolle rol’. De meeste interventies combineren verschillende werkzame elementen. Sommige combinaties van werkzame elementen komen vaak voor. Door afzonderlijke onderdelen van interventies in kaart te brengen, kan de werkzaamheid van elk element geëvalueerd worden. Het inzetten van een combinatie van werkzame elementen, en van algemene werkzame elementen zoals een goede uitvoering, kan de effectiviteit van interventies vergroten. Abstract Over the years, a wide range of loneliness interventions for older adults have been developed. The majority of these interventions are not effective in reducing loneliness. In order to gain more insight into why many interventions do not achieve the desired goal, we examine active elements that are used in interventions into reduce loneliness. In order to achieve this goal, intermediate goals are needed: to have a social network, a sense of belonging, to experience intimacy, to experience meaning. In order to arrive at a division into active elements, a qualitative analysis was carried out of 119 loneliness interventions, described in 22 reviews of interventions. The result is a division into seven active elements: ‘activities’, ‘meeting others’, practical support’, ‘meaningful contact’, ‘interpersonal skills’, ‘realistic expectations’ and ‘meaningful role’. Most interventions combine several active elements. Some combinations of active elements are common. By mapping out the individual components of interventions, the effectiveness of each element can be evaluated. The use of a combination of active elements, and of general active elements such as good execution, may increase the effectiveness of interventions.

Background: Childhood cancer survivors face high risks of adverse late health effects. Long-term follow-up care for childhood cancer survivors is crucial to improve their health and quality of life. However, implementation remains a challenge. To support implementation of high-quality long-term follow-up care, we explored expected barriers and facilitators for establishing this follow-up care among healthcare providers from four European clinics., Methods: A qualitative study was conducted using four focus groups comprising 30 healthcare providers in total. The semi-structured interview guide was developed based on the Grol and Wensing framework. Data was analyzed following a thematic analysis, combining both inductive and deductive approaches to identify barriers and facilitators across the six levels of Grol and Wensing: innovation, professional, patient, social, organizational and economic and political., Results: Most barriers were identified on the organizational level, including insufficient staff, time, capacity and psychosocial support. Other main barriers included limited knowledge of late effects among healthcare providers outside the long-term follow-up care team, inability of some survivors to complete the survivor questionnaire and financial resources. Main facilitators included motivated healthcare providers and survivors, a skilled hospital team, collaborations with important stakeholders like general practitioners, and psychosocial care facilities, utilization of the international collaboration and reporting long-term follow-up care results to convince hospital managers., Conclusion: This study identified several factors for successful implementation of long-term follow-up care for childhood cancer survivors. Our findings showed that specific attention should be given to knowledge, capacity, and financial issues, along with addressing psychosocial issues of survivors., (© 2024 The Author(s). Cancer Medicine published by John Wiley & Sons Ltd.)

Background: The objective of this study was to examine the prevalence of unhealthy lifestyle behaviors, overweight, and obesity in Dutch childhood cancer survivors (CCSs) compared with sibling controls and the Dutch general population. Other aims were to assess associated factors of unhealthy lifestyle behaviors, overweight, and obesity and to identify subgroups of CCSs at risk for these unhealthy statuses., Methods: The authors included 2253 CCSs and 906 siblings from the Dutch Childhood Cancer Survivor Study-Late Effects After Childhood Cancer cohort, part 1, and added data from the Dutch general population. Questionnaire data were collected on overweight and obesity (body mass index >25.0 kg/m 2 ), meeting physical activity guidelines (>150 minutes per week of moderate or vigorous exercises), excessive alcohol consumption (>14 and >21 alcoholic consumptions per week for women and men, respectively), daily smoking, and monthly drug use. Multivariable logistic regression analyses and two-step cluster analyses were performed to examine sociodemographic-related, health-related, cancer-related, and treatment-related associated factors of unhealthy lifestyle behaviors and to identify subgroups of CCSs at risk for multiple unhealthy behaviors., Results: CCSs more often did not meet physical activity guidelines than their siblings (30.0% vs. 19.3%; p < .001). Married as marital status, lower education level, nonstudent status, and comorbidities were common associated factors for a body mass index ≥25.0 kg/m 2 and insufficient physical activity, whereas male sex and lower education were shared associated factors for excessive alcohol consumption, daily smoking, and monthly drug use. A subgroup of CCSs was identified as excessive alcohol consumers, daily smokers, and monthly drug users., Conclusions: The current results emphasize the factors associated with unhealthy behaviors and the potential identification of CCSs who exhibit multiple unhealthy lifestyle behaviors., (© 2024 The Authors. Cancer published by Wiley Periodicals LLC on behalf of American Cancer Society.)

Background: Childhood, adolescent, and young adult (CAYA) cancer survivors, at risk for late effects, including cancer-related fatigue, cardiovascular issues, and psychosocial challenges, may benefit from interventions stimulating behaviour adjustments. Three nurse-led eHealth interventions (REVIVER) delivered via video calls and elaborating on person-centred care, cognitive behaviour therapy and/or motivational interviewing were developed. These interventions target: 1) fatigue management, 2) healthier lifestyle behaviours, and 3) self-efficacy and self-management. This study aimed to assess the feasibility and potential effectiveness of the REVIVER interventions for CAYA cancer survivors and healthcare professionals., Methods: In a single-group mixed methods design, CAYA cancer survivors aged 16-54, more than five years post-treatment, were enrolled. Feasibility, assessed via Bowen's outcomes for feasibility studies, included acceptability, practicality, integration and implementation, demand and adherence. Qualitative data from semi-structured interviews and a focus group interview with survivors and healthcare professionals supplemented the evaluation. Paired sample t-tests assessed changes in self-reported quality of life, fatigue, lifestyle, self-management, and self-efficacy at baseline (T0), post-intervention (T1), and 6-month follow-up (T2)., Results: The interventions and video consults were generally acceptable, practical, and successfully integrated and implemented. Success factors included the nurse consultant (i.e., communication, approach, and attitude) and the personalised approach. Barriers included sustainability concerns, technical issues, and short intervention duration. Regarding demand, 71.4%, 65.4%, and 100% of eligible CAYA cancer survivors engaged in the fatigue (N = 15), lifestyle (N = 17) and empowerment (N = 3) intervention, respectively, with 5, 5 and 2 participants interviewed, correspondingly. Low interest (demand) in the empowerment intervention (N = 3) and dropout rates of one-third for both fatigue and empowerment interventions were noted (adherence). Improvements in quality of life, fatigue (fatigue intervention), lifestyle (lifestyle intervention), self-efficacy, and self-management were evident among survivors who completed the fatigue and lifestyle interventions, with medium and large effect sizes observed immediately after the intervention and six months post-intervention., Conclusions: Our study demonstrates the feasibility of nurse-led video coaching (REVIVER interventions) despite lower demand for the empowerment intervention and lower adherence to the fatigue and empowerment interventions. The medium and high effect sizes found for those who completed the interventions hold potential clinical significance for future studies investigating the effectiveness of the REVIVER interventions., (© 2024. The Author(s).)

Background: Healthy behaviors are paramount in preventing long-term adverse health outcomes in childhood, adolescent, and young adult (CAYA) cancer survivors. We systematically reviewed and synthesized existing literature on barriers, facilitators, and other factors associated with health behaviors in this population., Methods: MEDLINE and PsycInfo were searched for qualitative and quantitative studies including survivors aged 16-50 years at study, a cancer diagnosis ≤25 years and ≥2 years post diagnosis. Health behaviors included physical activity, smoking, diet, alcohol consumption, sun exposure, and a combination of these behaviors (defined as health behaviors in general)., Results: Barriers, facilitators, and other factors reported in ≥2 two studies were considered relevant. Out of 4529 studies, 27 were included (n = 31,905 participants). Physical activity was the most frequently examined behavior (n = 12 studies), followed by smoking (n = 7), diet (n = 7), alcohol (n = 4), sun exposure (n = 4), and health behavior in general (n = 4). Relevant barriers to physical activity were fatigue, lack of motivation, time constraints, and current smoking. Relevant facilitators were perceived health benefits and motivation. Influence of the social environment and poor mental health were associated with more smoking, while increased energy was associated with less smoking. No relevant barriers and facilitators were identified for diet, alcohol consumption, and sun exposure. Barriers to healthy behavior in general were unmet information needs and time constraints whereas lifestyle advice, information, and discussions with a healthcare professional facilitated healthy behavior in general. Concerning other factors, women were more likely to be physically inactive, but less likely to drink alcohol and more likely to comply with sun protection recommendations than men. Higher education was associated with more physical activity, and lower education with more smoking., Conclusion: This knowledge can be used as a starting point to develop health behavior interventions, inform lifestyle coaches, and increase awareness among healthcare providers regarding which survivors are most at risk of unhealthy behaviors., (© 2024 The Author(s). Cancer Medicine published by John Wiley & Sons Ltd.)

The current study investigated effects of dietary amino acid (AA) availability on lactational body condition loss and metabolic status, in relation to reproductive parameters after weaning up to Day 8 post-ovulation. Primiparous sows (n = 35) were allocated to one of two lactation diets containing either low crude protein (CP, 140 g/kg) with a low percentage (8%) of slow protein in total protein (LL, n = 18) or high CP (180 g/kg) with a high (16%) percentage of slow protein (HH, n = 17). The HH diet was expected to improve AA utilization by supplying more AA, in a more gradual fashion. The diets did not affect sow body condition loss during lactation, while the HH diet tended to increase litter weight gain during the week 3 of lactation (Δ = 1.3 kg, P = 0.09). On Day 14 post-farrowing, HH diet led to higher plasma urea both pre-feeding and post-feeding (Δ = 2.3 mmol/L, P < 0.01, Δ = 2.4 mmol/L, P < 0.01, respectively), whilst plasma creatinine, NEFA and IGF-1 were similar. No dietary effects on reproductive parameters were found, however several relationships were found between body condition and reproductive parameters. Sows with higher body weight on Day 1 or Day 21 post-farrowing had greater follicle size on Day 3 post-weaning (β = 0.03 mm/kg, P < 0.01, β = 0.04 mm/kg, P < 0.01, respectively). At Day 8 post-ovulation, plasma progesterone concentration was negatively related to loin muscle loss (β = -0.67 ng/ml · mm -1 , P = 0.02), backfat loss (β = -2.33 ng/ml · mm -1 , P = 0.02), and estimated body fat loss (β = -0.67 ng/ml · mm -1 , P = 0.02). Both plasma progesterone and the number of corpora lutea were positively related to the energy balance during lactation (β = 0.03 ng/ml · ME MJ -1 , P = 0.01, β = 0.01 CL/ME MJ, P = 0.02, respectively). The conceptus size at Day 8 post-ovulation was negatively related to body weight loss (β = -0.01 mm/kg, P = 0.01), estimated body fat loss (β = -0.02 mm/kg, P = 0.03) and estimated body protein loss (β = -0.06 mm/kg, P = 0.04), and was positively related to the energy balance during lactation (β = 5.2*10 -4  mm/ME MJ, P = 0.01). In conclusion, body protein and fat losses during lactation reduced subsequent plasma progesterone concentration and conceptus development at Day 8 post-ovulation., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Aziridines are important structural motifs and intermediates, and several synthetic strategies for the direct aziridination of alkenes have been introduced. However, many of these strategies require an excess of activated alkene, suffer from competing side-reactions, have limited functional group tolerance, or involve precious transition metal-based catalysts. Herein, we demonstrate the direct aziridination of alkenes by combining sulfonyl azides as a triplet nitrene source with a catalytic amount of an organic dye functioning as photosensitizer. We show how the nature of the sulfonyl azide, in combination with the triplet-excited state energy of the photosensitizer, affects the aziridination yield and provide a mechanistic rationale to account for the observed dependence of the reaction yield on the nature of the organic dye and sulfonyl azide reagents. The optimized reaction conditions enable the aziridination of structurally diverse and complex alkenes, carrying various functional groups, with the alkene as the limiting reagent.

Background: Healthy behaviors, that is, engaging in regular physical activities, maintaining a healthy diet, limiting alcohol consumption, and avoiding tobacco and drug use, decrease the risk of developing late adverse health conditions in childhood cancer survivors. However, childhood cancer survivors may experience barriers to adopting and maintaining healthy behaviors. This study aimed to assess these barriers and facilitators to health behavior adoption and maintenance in childhood cancer survivors., Methods: A focus group ( n  = 12) and semi-structured telephone interviews ( n  = 20) were conducted with a selected sample of European and Dutch childhood cancer survivors, respectively. The Theoretical Domains Framework (TDF) was used to inform the topic guide and analysis. Inductive thematic analysis was applied to identify categories relating to barriers and facilitators of health behavior adoption and maintenance, after which they were deductively mapped onto the TDF., Results: Ten TDF domains were identified in the data of which "Knowledge," "Beliefs about consequences," "Environmental context and resources," and "Social influences" were most commonly reported. Childhood cancer survivors expressed a need for knowledge on the importance of healthy behaviors, possibly provided by healthcare professionals. They indicated physical and long-term benefits of healthy behaviors, available professional support, and a supporting and health-consciously minded work and social environment to be facilitators. Barriers were mostly related to a lack of available time and an unhealthy environment. Lastly, (social) media was perceived as both a barrier and a facilitator to healthy behaviors., Conclusion: This study has identified education and available professional support in health behaviors and the relevance of healthy behaviors for childhood cancer survivors as key opportunities for stimulating health behavior adoption in childhood cancer survivors. Incorporating health behavior support and interventions for this population should therefore be a high priority., (© 2023 The Authors. Cancer Medicine published by John Wiley & Sons Ltd.)

Background: Childhood cancer survivors (CCSs) have an increased risk of developing chronic health conditions. Evidence suggests that poor health behaviors further increase health risks. Healthcare professionals (HCPs) involved in survivorship care have a key role in providing health behavior support (HBS) but can feel limited in their ability to do so. This study aims to explore European HCPs perceived facilitators and barriers to providing HBS to CCSs., Methods: Five focus groups with 30 HCPs from survivorship care clinics across Europe were conducted. Topic guides were informed by the Theoretical Domains Framework (TDF) to capture domains that may influence provision of HBS. Focus groups were analyzed with thematic analysis. Transcripts were inductively coded, after which axial coding was applied to organize codes into categories. Finally, categories were mapped onto the TDF domains., Results: Nine TDF domains were identified in the data. The most commonly reported TDF domains were "Knowledge", "Skills", and "Environmental context and resources". HCPs indicated that their lack of knowledge of the association between late effects and health behaviors, besides time restrictions, were barriers to HBS. Facilitators for HBS included possession of skills needed to pass on health behavior information, good clinic organization, and an established network of HCPs., Conclusions: This study identified education and training of HCPs as key opportunities to improve HBS. Survivorship care clinics should work towards establishing well-integrated structured care with internal and external networks including HBS being part of routine care. Proper understanding of facilitators and barriers should lead to better survivorship care for CCSs., (© 2022 The Authors. Cancer Medicine published by John Wiley & Sons Ltd.)

Background: Physical inactivity and unhealthy dietary habits are known to be disadvantageous for the development of late adverse effects in survivors of childhood, adolescent, and young adult cancer. To make interventions, aimed at improving lifestyle, fit into the daily life of survivors, interventions should be designed and delivered in a person-centred way with a limited time burden. As part of the European PanCareFollowUp project, an eHealth intervention was developed to support sustainable changes to physical activity levels and/or diet of childhood, adolescent, and young adult cancer survivors. This feasibility study aims to gain insight into the feasibility and potential effect sizes of the PanCareFollowUp lifestyle intervention., Methods: The PanCareFollowUp lifestyle intervention consists of person-centred 3-6 screen-to-screen sessions with a certified lifestyle coach. The intervention will be evaluated with a single-arm pre-post feasibility study conducted at two survivorship care clinics in the Netherlands. A total of 60 participants who are (i) diagnosed with cancer <25 years, (ii) ≥ 5 years post-treatment, (iii) aged 16-55 years, and (iv) have a low physical activity level and/or unhealthy dietary intake manifested by overweight will be recruited. Using reports, hospital records, and questionnaires for survivors, coaches, and late effect doctors, feasibility will be based on (i) adherence to intervention, (ii) acceptability, (iii) practicality, (iv) integration/implementation, (v) demand, and (vi) attrition. The potential effect sizes of the intervention will be explored by determining the percentage of survivors that reach the personalized lifestyle goals that were set with the coach. Physical activity level, dietary intake, BMI, general self-efficacy, self-management, and motivation level will be assessed at three time points with questionnaires, reports, and/or an accelerometer., Discussion: Data of this study will be gathered to assess the feasibility and potential effect sizes. This will allow for further intervention refinement as needed as well as to inform a future large-scale intervention study and a manual for implementation at other centres., Trial Registration: International Clinical Trial Registry Platform (ICTRP) number: NL8932 (ICTRP Search Portal (who.int)). Registered on September 29, 2020., (© 2022. The Author(s).)

The formation of Co(III)-thiolate complexes from Co(II)-disulfide complexes using the anionic ligand 8-quinolinolate (quin - ) has been studied experimentally and quantum chemically. Two Co(II)-disulfide complexes [Co 2 (L x SSL x )(Cl) 4 ] ( x = 1 or 2; L 1 SSL 1 = 2,2'-disulfanediylbis( N , N -bis(pyridin-2-ylmethyl)ethan-1-amine; L 2 SSL 2 = 2,2'-disulfanedylbis ( N -((6-methylpyridin-2-yl)methyl)- N -(pyridin-2-ylmethyl) ethan-1-amine) have been successfully converted with high yield to their corresponding Co(III)-thiolate complexes upon addition of the ligand 8-quinolinolate. Using density functional theory (DFT) computations the d-orbital splitting energies of the cobalt-thiolate compounds [Co(L 1 S)(quin)] + and [Co(L 2 S)(quin)] + were estimated to be 3.10 eV and 3.07 eV, indicating a slightly smaller ligand-field strength of ligand L 2 SSL 2 than of L 1 SSL 1 . Furthermore, the orientation of the quin - ligand in the thiolate compounds determines the stability of the thiolate complex. DFT computations show that the thiolate structure benefits from more electrostatic attraction when the oxygen atom of the quin - ligand is positioned trans to the sulfur atom of the [Co(L 1 S)] 2+ fragment. Quin - is the first auxiliary ligand with which it appeared possible to induce the redox-conversion reaction in cobalt(II) compounds of the relatively weak-field ligand L 2 SSL 2 .

The redox-conversion reaction of cobalt(II)-disulfide to cobalt(III)-thiolate complexes triggered by addition of the bidentate ligand 2,2'-bipyridine has been investigated. Reaction of the cobalt(II)-disulfide complex [Co 2 (L 1 SSL 1 )(X) 4 ] (L 1 SSL 1 = di-2-(bis(2-pyridylmethyl)amino)-ethyldisulfide; X = Cl or Br) [1X] with 2,2'-bipyridine (bpy) resulted in the formation of two different products, namely the cobalt(III)-thiolate complex [Co(L 1 S)(bpy)]X 2 and the unexpected side product [Co 2 (L 1 SSL 1 )(bpy) 2 (X) 2 ]X 2 . Crystals of [Co 2 (L 1 SSL 1 )(bpy) 2 (Cl) 2 ](BPh 4 ) 2 [2Cl](BPh 4 ) 2 obtained after anion exchange showed the cobalt(II) ions to be in octahedral geometries with the nitrogen donors of the disulfide ligand arranged in a facial conformation and the chloride ion trans to the tertiary amine nitrogen. Remarkably, this side product cannot be converted to the cobalt(III)-thiolate compound [Co(L 1 S)(bpy)](SbF 6 ) 2 [3](SbF 6 ) 2 by removal of the chloride ion with use of a silver salt, as this causes scrambling of the ligands, resulting in the formation of [Co(bpy) 3 ] n + . [Co(L 1 S)(bpy)](SbF 6 ) 2 was obtained in a pure form by addition of bpy to a solution in acetonitrile of the compound [Co(L 1 S)(MeCN) 2 ] 2+ [4] 2+ . Addition of NEt 4 Cl to [3](SbF 6 ) 2 regenerates the cobalt(II)-disulfide complex [1Cl] as confirmed spectroscopically. DFT studies revealed that the conversion from [1Cl] to [3] 2+ most likely occurs via the hypothetical intermediate species [2Cl] 2+ mer , in which the nitrogen atoms of the disulfide ligand are arranged in a meridional conformation. Interestingly, the estimated d-orbital splitting energy of [3] 2+ is lower than that of [4] 2+ , indicating that the ligand-field strength of bpy is lower than anticipated, which hampers clean conversion in the redox-conversion reaction. This study shows that the redox-conversion reaction between cobalt(II)-disulfide and cobalt(III)-thiolate complexes is intricate rather than straightforward.

Background: The majority of childhood cancer survivors are at risk of treatment-related adverse health outcomes. Survivorship care to mitigate these late effects is endorsed, but it is not available for many adult survivors of childhood cancer in Europe. The PanCareFollowUp project was initiated to improve their health and quality of life (QoL) by facilitating person-centred survivorship care., Methods: The PanCareFollowUp consortium was established in 2018, consisting of 14 project partners from ten European countries, including survivor representatives. The consortium will develop two PanCareFollowUp Interventions, including a person-centred guideline-based model of care (Care Intervention) and eHealth lifestyle coaching (Lifestyle Intervention). Their development will be informed by several qualitative studies and systematic reviews on barriers and facilitators for implementation and needs and preferences of healthcare providers (HCPs) and survivors. Implementation of the PanCareFollowUp Care Intervention as usual care will be evaluated prospectively among 800 survivors from Belgium, Czech Republic, Italy and Sweden for survivor empowerment, detection of adverse health conditions, satisfaction among survivors and HCPs, cost-effectiveness and feasibility. The feasibility of the PanCareFollowUp Lifestyle Intervention will be evaluated in the Netherlands among 60 survivors., Results: Replication manuals, allowing for replication of the PanCareFollowUp Care and Lifestyle Intervention, will be published and made freely available after the project. Moreover, results of the corresponding studies are expected within the next five years., Conclusions: The PanCareFollowUp project is a novel European collaboration aiming to improve the health and QoL of all survivors across Europe by developing and prospectively evaluating the person-centred PanCareFollowUp Care and Lifestyle Interventions., Competing Interests: Conflict of interest statement The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Background: Successful cancer treatment can lead to cancer survivors being predisposed to an increased lifelong risk of adverse late health effects. Therefore, high-quality cancer survivorship care to earlier detect and treat late effects or to preserve survivor's health is essential. Nevertheless, this care needs to be sustainable and cost-effective as well. We developed three different screen-to-screen nurse-led eHealth interventions for survivors of childhood, adolescent and young adult-onset cancer, collectively called the REVIVER interventions. Elaborating on person-centred care principles with content based on cognitive behavioural therapy modules and/or motivational interviewing techniques, these interventions aim to empower and coach survivors to improve (1) symptoms of cancer-related fatigue, (2) self-efficacy and self-management or (3) lifestyle. With the REVIVER study, we aim to evaluate the interventions' feasibility and gain insights into the potential effectiveness., Methods: The REVIVER study involves a mixed methods design, including (1) interviews till data saturation with cancer survivors who completed the interventions as well as with all involved medical professionals, (2) reviews of nurses reports and (3) a single-group, pre-post evaluation among cancer survivors. Eligible survivors are survivors of childhood, adolescent and young adult-onset cancer who are referred to one of the interventions, in complete remission of cancer, 16-44 years old at enrolment, completed treatment at least 5 years ago and have access to a device with Internet options. We will assess feasibility in terms of demand, adherence, acceptability, practicality and integration/implementation. Health-related quality of life, as primary outcome of the potential effectiveness evaluation, will be assessed at three different time points: prior to the intervention; immediately following the intervention and 6 months post-intervention. Secondary outcome measures include changes in level of fatigue, self-efficacy, self-management and lifestyle., Discussion: This is the first study to evaluate the feasibility and potential effectiveness of eHealth nurse-led interventions elaborating on person-centred care, using cognitive behavioural therapy and/or motivational interviewing techniques as an innovative and promising approach for providing CAYA cancer survivorship care. If the interventions prove to be feasible and potential effective, a randomized controlled trial will be conducted to test the (cost)-effectiveness., Competing Interests: Competing interestsThe authors declare that they have no competing interests., (© The Author(s). 2019.)

The redox interconversion between Co(III) thiolate and Co(II) disulfide compounds has been investigated experimentally and computationally. Reactions of cobalt(II) salts with disulfide ligand L 1 SSL 1 (L 1 SSL 1 = di-2-(bis(2-pyridylmethyl)amino)-ethyl disulfide) result in the formation of either the high-spin cobalt(II) disulfide compound [Co II 2 (L 1 SSL 1 )Cl 4 ] or a low-spin, octahedral cobalt(III) thiolate compound, such as [Co III (L 1 S)(MeCN) 2 ](BF 4 ) 2 . Addition of thiocyanate anions to a solution containing the latter compound yielded crystals of [Co III (L 1 S)(NCS) 2 ]. The addition of chloride ions to a solution of [Co III (L 1 S)(MeCN) 2 ](BF 4 ) 2 in acetonitrile results in conversion of the cobalt(III) thiolate compound to the cobalt(II) disulfide compound [Co II 2 (L 1 SSL 1 )Cl 4 ], as monitored with UV-vis spectroscopy; subsequent addition of AgBF 4 regenerates the Co(III) compound. Computational studies show that exchange by a chloride anion of the coordinated acetonitrile molecule or thiocyanate anion in compounds [Co III (L 1 S)(MeCN) 2 ] 2+ and [Co III (L 1 S)(NCS) 2 ] induces a change in the character of the highest occupied molecular orbitals, showing a decrease of the contribution of the p orbital on sulfur and an increase of the d orbital on cobalt. As a comparison, the synthesis of iron compounds was undertaken. X-ray crystallography revealed that structure of the dinuclear iron(II) disulfide compound [Fe II 2 (L 1 SSL 1 )Cl 4 ] is different from that of cobalt(II) compound [Co II 2 (L 1 SSL 1 )Cl 4 ]. In contrast to cobalt, reaction of ligand L 1 SSL 1 with [Fe(MeCN) 6 ](BF 4 ) 2 did not yield the expected Fe(III) thiolate compound. This work is an unprecedented example of redox interconversion between a high-spin Co(II) disulfide compound and a low-spin Co(III) thiolate compound triggered by the nature of the anion.

Four dimeric nickel(II) complexes [Ni 2 Cl 2 (BnC 2 S) 2 ] [ 1 ], [Ni 2 Cl 2 (BnC 3 S) 2 ] [ 2 ], [Ni 2 (PyC 2 S) 2 ]Br 2 [ 3 ]Br 2 , and [Ni 2 (PyC 3 S) 2 ]Br 2 [ 4 ]Br 2 of four different thiolate-functionalized N-heterocyclic carbene (NHC) ligands were synthesized, and their structures have been determined by single-crystal X-ray crystallography. The four ligands differ by the alkyl chain length between the thiolate group and the benzimidazole nitrogen (two -C 2 - or three -C 3 - carbon atoms) and the second functionality at the NHC being a benzyl (Bn) or a pyridylmethyl (Py) group. The nickel(II) ions are coordinated to the NHC carbon atom and the pendent thiolate group, which bridges to the second nickel(II) ion creating the dinuclear structure. Additionally, in compounds [ 1 ] and [ 2 ], the fourth coordination position of the square-planar Ni(II) centers is occupied by the halide ions, whereas in [ 3 ] 2+ and [ 4 ] 2+ , the additional pendant pyridylmethyl groups complete the coordination spheres of the nickel ions. The electrochemical properties of the four complexes were studied using cyclic voltammetry and controlled-potential coulometry methods. The thiolate-functionalized carbene complexes [ 1 ] and [ 2 ] appear to be poor electrocatalysts for the hydrogen evolution reaction; the complexes [ 3 ]Br 2 and [ 4 ]Br 2 , bearing an extra pyridylmethyl group, show higher catalytic activity in proton reduction, indicating that the pyridine group plays an important role in the catalytic cycle., Competing Interests: The authors declare no competing financial interest.

Ethene is a highly diffusive and relatively unreactive gas that induces aging responses in plants in concentrations as low as parts per billion. Monitoring concentrations of ethene is critically important for transport and storage of food crops, necessitating the development of a new generation of ultrasensitive detectors. Here we show that by functionalizing graphene with copper complexes biologically relevant concentrations of ethene and of the spoilage marker ethanol can be detected. Importantly, in addition these sensors provide us with important insights into the interactions between molecules, a key concept in chemistry. Chemically induced dipole fluctuations in molecules as they undergo a chemical reaction are harvested in an elegant way through subtle field effects in graphene. By exploiting changes in the dipole moments of molecules that occur upon a chemical reaction we are able to track the reaction and provide mechanistic insight that was, until now, out of reach.

The two heterodinuclear nickel-ruthenium complexes [Ni(xbSmS)RuCp(PPh 3 )]PF 6 and [Ni(xbSmSe)RuCp(PPh 3 )]PF 6 (H 2 xbSmS = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene, H 2 xbSmSe = 1,2,-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene, Cp = cyclopentadienyl) were synthesized as biomimetic models of [NiFe] and [NiFeSe] hydrogenases. The X-ray structural analyses of the complexes show that the two NiRu complexes are isomorphous; in both NiRu complexes the nickel(ii) centers are coordinated in a square-planar environment with two thioether donor atoms and two thiolate or selenolate donors that are bridging to the ruthenium(ii) center. The Ru(ii) ion is further coordinated to a η 5 -cyclopentadienyl group and a triphenylphosphane ligand. These complexes catalyze hydrogen evolution in the presence of acetic acid in acetonitrile solution at around -2.20 V vs. Fc + /Fc with overpotentials of 810 and 830 mV, thus they can be regarded as functional models of the [NiFe] and [NiFeSe] hydrogenases.

Two new heterodinuclear nickel-iron complexes [Ni(pbSmSe)FeCpCO]PF 6 and [Ni(xbSmSe)FeCpCO]PF 6 were synthesized as mimics of the [NiFeSe] hydrogenase active site (HCp = cyclopentadiene; H 2 pbSmSe = 1,9-diselenol-3,7-dithia-2,2,8,8-tetramethylnonane; H 2 xbSmSe = 1,2,-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene). The compounds were characterized by single crystal X-ray diffraction and cyclic voltammetry. X-ray structure determinations showed that in both NiFe complexes the nickel(ii) center is in a square-planar S 2 Se 2 environment; the two selenolate donors are bridging to the iron(ii) center that is further coordinated to an η 5 -cyclopentadienyl group and a carbon monoxide ligand. Electrochemical studies showed that the complex [Ni(pbSmSe)FeCpCO]PF 6 is an electrocatalyst for the production of H 2 in DMF in the presence of acetic acid at -2.1 V vs. Fc + /Fc; a foot-of-the-wave (FOWA) analysis of the catalytic currents yielded an estimation of k obs of 24 s -1 .

The synthesis and characterization, using NMR ( 1 H and 13 C), infrared spectroscopy, and X-ray crystallography, of the ethene and carbon monoxide copper(i) complexes of hydridotris(3,5-diphenylpyrazol-1-yl)borate ([Tp Ph 2 ] - ) and the two new ligands hydridotris(3,5-bis(1-naphthyl)pyrazol-1-yl)borate ([Tp (1Nt) 2 ] - ) and hydridotris(3,5-bis-(2-naphthyl)pyrazol-1-yl)borate ([Tp (2Nt) 2 ] - ) are described. X-ray crystal structures are presented of [Cu(Tp Ph 2 )(C 2 H 4 )] and [Cu(Tp (2Nt) 2 )(C 2 H 4 )]. The compound [Cu(Tp Ph 2 )(C 2 H 4 )] features interactions between the protons of the ethene ligand and the π-electron clouds of the phenyl substituents that make up the binding pocket surrounding the copper(i) center. These dipolar interactions result in strongly upfield shifted signals of the ethene protons in 1 H-NMR. [Cu(Tp (1Nt) 2 )(CO)] and [Cu(Tp (2Nt) 2 )(CO)] were examined using infrared spectroscopy and were found to have CO stretching vibrations at 2076 and 2080 cm -1 respectively. The copper(i) carbonyl complexes form self-assembled monolayers when drop cast onto HOPG and thin multilayers of a few nanometers thickness when dip coated onto graphene. General macroscopic trends such as the different tendencies to crystallize observed in the complexes of the two naphthyl-substituted ligands appear to extend well to the nanoscale where a well-organized monolayer could be observed of [Cu(Tp (2Nt) 2 )(CO)].

Despite being a simple dehydration reaction, the industrially relevant conversion of lactic acid to acrylic acid is particularly challenging. For the first time, the catalytic cracking of lactide and poly(lactic acid) to acrylic acid under mild conditions is reported with up to 58 % yield. This transformation is catalyzed by strong acids in the presence of bromide or chloride salts and proceeds through simple S N 2 and elimination reactions., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Recently, the addition of negatively charged liposomes was shown to increase the quantum yield of the photocatalytic reduction of 5,5'-dithio(2-nitrobenzoic acid) (H 2 DTNB) to 2-nitro-5-thiobenzoic acid (H 2 NTB) by triethanolamine using meso-tetra(4-(N-methylpyridinium)porphyrinato zinc chloride as photosensitizer. In this work, we investigate in detail the kinetics of this photocatalytic reaction both in homogeneous solution and at the surface of negatively charged liposomes, to unravel the effects of liposomes on the mechanism of the photoreaction. In homogeneous solution, the reaction is initiated by oxidative quenching. Both static (singlet) and dynamic (triplet) quenching of the photosensitizer contribute to the formation of the photoproduct. In these conditions, the reaction is limited by the low efficiency of reductive regeneration of the photosensitizer, compared to charge recombination. Upon adsorption of the positively charged photosensitizer to the negative surface of the liposomes, however, both static and dynamic oxidative quenching become ineffective due to electrostatic repulsion of the dianionic DTNB 2- from the negatively charged membrane. In such conditions, photoreduction occurs via reductive quenching, showing that the addition of liposomes can truly modify the mechanism of photocatalyzed redox reactions.

Reduced summer farrowing rates may be due to inadequate corpora luteal (CL) support. Porcine CL become dependent on LH from 12 d of pregnancy and the embryonic estrogen signal for maternal recognition of pregnancy (MRP) is initiated at about 11-12 d after insemination. We hypothesised that injection of the LH analogue human chorionic gonadotropin (hCG) would induce growth of estrogenic follicles and, by mimicking the signal for MRP and stimulating progesterone secretion, increase primiparous sow fertility. In Experiment 1, during a 28 d lactation 53 mixed parity sows were full-fed either throughout lactation (n=16) or until 18 d and then feed restricted during the last 10 d of lactation (n=36). At 12 d after mating restrict-fed sows were injected with 1000IU hCG (n=17) or were not injected (n=19); the full-fed sows acted as non-treated positive controls. Transrectal ovarian ultrasound exams were performed on days 12, 16, 20, 24, and 28; blood samples were obtained on days 12, 14, and 15 for estradiol and progesterone assay. For Experiment 2, during the summer months primiparous sows received 1000IU hCG 12 d after mating (n=28) or were non-injected controls (n=27). Pregnancy status was determined at 28 d and sows allowed to go to term to determine farrowing rates and litter sizes. In Experiment 1, injection of hCG increased (P<0.001) follicle diameter and serum concentrations of estradiol (P<0.01) and progesterone (P<0.05). There were no effects of lactation feeding level on wean-estrus interval, farrowing rate or subsequent litter size. In Experiment 2, hCG injection was associated with a higher pregnancy rate (P<0.05) and farrowing rate (P<0.08). There was no effect on litter size. These data confirm that hCG stimulates growth of estrogenic follicles and CL function, and improves primiparous sow fertility during the summer months., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Liposomes are interesting scaffolds for photocatalysis. In particular, charged liposomes were shown to increase the quantum efficiency of photocatalytic reactions involving charged porphyrin photosensitizers and charged electron acceptors. In this work, the effects of adding positively charged liposomes (DMPC/eDMPCCl 1:1) on the mechanism of the photocatalytic reduction of methyl viologen (MV(2+)) by cysteine in the presence of sodium meso-tetra-(4-sulfonato)porphyrinatozinc (Na41) were probed by modeling UV-vis spectroscopy data using a steady-state approximation. By varying the concentration of methyl viologen, we found that the liposomes not only prevent the formation of a 1:1 complex between ground-state photosensitizer 1(4-) and MV(2+) but also that they increase the cage-escape yield in the excited state. Furthermore, the electrostatic repulsion between the liposomes and MV(2+) diminishes by 1 order of magnitude the rate of oxidative quenching of the photosensitizer triplet excited state ((T)1(4-)) by MV(2+). By varying the amount of sacrificial electron donor (cysteine), the effect of liposome addition on the charge recombination reactions could also be studied. Because of the positive charge borne by the photoproduct MV(•+), it was also repelled from the membrane, which significantly slows charge recombination at the surface of the liposome. Overall, compared to a liposome-free solution, the rates of most elementary steps of the photocatalytic reduction of MV(2+) by cysteine are strongly modified when the negative photosensitizer is adsorbed on a positively charged liposome surface. These results not only explain the much higher efficiency of the liposome-containing system but also illustrate the power of supramolecular chemistry for the tuning of photocatalysis.

A one-step direct solvothermal synthesis of an Ln metal-organic framework (MOF) film is reported. The LnHL (Ln = Tb and Gd) films that were deposited on a Gd2O3 subtrate are continuous and smooth. The Gd0.9Tb0.1HL film can be used as a ratiometric thermometer, showing good linear behaviour in the temperature range of 110-250 K with a sensitivity up to 0.8% K(-1).

The tetrapyridyl ligand bbpya (bbpya=N,N-bis(2,2'-bipyrid-6-yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)2 ] (1) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai's domain model, and powder X-ray diffraction measurements, 1 is low-spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T1/2 =418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong NH⋅⋅⋅S intermolecular H-bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1. DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N'-di(pyrid-2-yl)-2,2'-bipyridine-6,6'-diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)2 ] (2). Periodic DFT calculations suggest that crystal-packing effects are significant for compound 2, in which they destabilize the HS state by about 1500 cm(-1) . The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The ethene and carbon monoxide adducts of copper(I) with seven trispyrazolylborate ligands ([HB(3-CF3-5-{4-RPh}pz)3](-); R = NO2 (4a), CF3 (4b), Cl (4c), F (4d), H (4e), OMe (4f) and NMe2 (4g)) were synthesized and characterized. The ligands were synthesized from their corresponding pyrazoles and sodium tetrahydridoborate and were obtained as solvent adducts of their sodium salts after workup. When the pyrazole with the most electron-withdrawing substituent (R = NO2) is used the asymmetric ligand [HB(3-CF3-5-{4-NO2Ph}pz)2(3-{4-NO2Ph}-5-CF3pz)](-) (4a') is formed as the major product. Copper(I) complexes with ethene or CO as a co-ligand were prepared in good yields and were structurally characterized using (1)H NMR, (13)C NMR and infrared spectroscopy. Single crystal X-ray crystallography analyses revealed the structures of Na4a', Na4b, four copper ethene complexes and four copper carbonyl complexes. The structures of the copper(I) complexes show Cu(I) ions in pseudo-tetrahedral coordination environments consisting of three nitrogen atoms of the trispyrazolylborate ligand and the carbonyl or η(2)-coordinated ethene ligands, with nearly identical coordination environments around the Cu(I) ion. The compound [Na(4a')(H2O)]n crystallizes as one-dimensional chains with intermolecular NaO2N interactions. The sodium ions were found in severely distorted octahedral geometries with three nitrogen atoms from the trispyrazolylborate ligand, one aqua ligand and two oxygen atoms from the nitro group of an adjacent molecule. The compound [Na2(4b)2(μ-H2O)2] crystallizes as a centrosymmetric water-bridged dimer: two five-coordinate square-pyramidal sodium ions each are coordinated facially by three nitrogen atoms from a trispyrazolylborate ligand and two bridging water ligands. Below the base of the pyramidal structure one intermolecular and two intramolecular NaF short contacts are present. The (1)H and (13)C NMR spectra of the copper-ethene complexes show signals for the ethene ligands in the range of 4.84-4.96 ppm and 84.9-86.8 ppm respectively. The infrared spectra of the carbonyl complexes show CO stretching frequencies in the range of 2096-2120 cm(-1). Both the NMR signals for the ethene ligands and infrared signals for the carbonyl ligands were found to show good correlations with the Hammett σp parameters of the substituents on the phenyl rings of the ligands.

Unidirectional photocatalytic electron transfer from a hydrophilic electron donor encapsulated in the interior of a liposome, to a hydrophilic electron acceptor on the other side of the membrane, has been achieved using the simple membrane-soluble electron relay 1-methoxy-N-methylphenazinium (MMP(+)). The total amount of photoproduct (>140 nmol) exceeds the number of moles of MMP(+) present (125 nmol), thus showing that the transport of electrons is catalytic.

A ratiometric thermometer based on a mixed-metal Ln(III) metal-organic framework is reported that has good sensitivity in a wide temperature range from 4 to 290 K and a quantum yield of 22% at room temperature. The sensing mechanism in the europium-doped compound Tb0.95Eu0.05HL (H4L = 5-hydroxy-1,2,4-benzenetricarboxylic acid) is based not only on phonon-assisted energy transfer from Tb(III) to Eu(III) centers, but also on phonon-assisted energy migration between neighboring Tb(III) ions. It shows good performance in a wide temperature range, especially in the range 4-50 K, reaching a sensitivity up to 31% K(-1) at 4 K.

A large library of Cu(II) complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu···Cu distances and the formation of polymeric species. Comparison of the 3,5-DTBC oxidation rates showed that ligands that stabilize the biomimetic dinuclear Cu(II) μ-thiolate complex also result in copper compounds that are much more active in the oxidation of 3,5-DTBC. This oxidation activity is however inhibited by the presence of chloride ions. The highest kcat that was observed was 6900 h(-1), which is one of the highest turnover frequencies reported so far for catechol oxidation in CH3CN.

The proton-induced electron-transfer reaction of a Cu(II) μ-thiolate complex to a Cu(I) -containing species has been investigated, both experimentally and computationally. The Cu(II) μ-thiolate complex [Cu(II) 2 (L(Me) S)2 ](2+) is isolated with the new pyridyl-containing ligand L(Me) SSL(Me) , which can form both Cu(II) thiolate and Cu(I) disulfide complexes, depending on the solvent. Both the Cu(II) and the Cu(I) complexes show reactivity upon addition of protons. The multivalent tetranuclear complex [Cu(I) 2 Cu(II) 2 (LS)2 (CH3 CN)6 ](4+) crystallizes after addition of two equivalents of strong acid to a solution containing the μ-thiolate complex [Cu(II) 2 (LS)2 ](2+) and is further analyzed in solution. This study shows that, upon addition of protons to the Cu(II) thiolate compound, the ligand dissociates from the copper centers, in contrast to an earlier report describing redox isomerization to a Cu(I) disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated Cu(II) μ-thiolate and Cu(I) disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [Cu(I) (CH3 CN)4 ](+) and protonated ligand is energetically favored over conversion to a protonated Cu(I) disulfide complex., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The redox equilibrium between dinuclear Cu(II) μ-thiolate and Cu(I) disulfide structures has been analyzed experimentally and via DFT calculations. Two new ligands, L(2)SSL(2) and L(4)SSL(4), and their Cu(II) μ-thiolate and Cu(I) disulfide complexes were synthesized. For L(2)SSL(2), these two redox-isomeric copper species are shown to be in equilibrium, which depends on both temperature and solvent. For L(4)SSL(4) the μ-thiolate species forms as the kinetic product and further evolves into the disulfide complex under thermodynamic control, which creates the unprecedented possibility to compare both species under the same reaction conditions. The energies of the μ-thiolate and disulfide complexes for two series of related ligands have been calculated with DFT; the results rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in the formation of the Cu(II) thiolate structure.

Photocatalytic systems often suffer from poor quantum yields due to fast charge recombination: The energy-wasting annihilation of the photochemically created charge-separated state. In this report, we show that the efficiency of photoinduced electron transfer from a sacrificial electron donor to positively charged methyl viologen, or to negatively charged 5,5'-dithiobis(2-nitrobenzoate), increases dramatically upon addition of charged phospholipid vesicles if the charge of the lipids is of the same sign as that of the electron acceptor. Centrifugation and UV/Vis titration experiments showed that the charged photosensitizers adsorb at the liposome surface, that is, where the photocatalytic reaction takes place. The increased photoelectron transfer efficiency in the presence of charged liposomes has been ascribed to preferential electrostatic interactions between the photosensitizer and the membrane, which prevents the formation of photosensitizer-electron-acceptor complexes that are inactive towards photoreduction. Furthermore, it is shown that the addition of liposomes results in a decrease in photoproduct inhibition, which is caused by repulsion of the reduced electron acceptor by the photocatalytic site. Thus, liposomes can be used as a support to perform efficient photocatalysis; the charged photoproducts are pushed away from the liposomes and represent "soluble electrons" that can be physically separated from the place where they were generated., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The conversion of γ-valerolactone (GVL) in three atom-efficient steps to the important polymer precursor ε-caprolactam is reported. The bio-based GVL can be converted to a mixture of isomeric methyl pentenoates (MP) via trans-esterification with methanol with 94% yield (ratio of 3-MP/4-MP=3:1); subsequent aminolysis with ammonia leads to a mixture of pentenamides (PA) almost quantitatively (99% conversion). The resulting pentenamides are ultimately converted into ε-caprolactam via a rhodium-catalyzed intramolecular hydroamidomethylation reaction, comprising an initial hydroformylation of the alkene moiety of PA and subsequent ring-closing reductive amidation of the resulting aldehyde with the amide functionality. A promising yield of caprolactam of about 90% can be obtained with a Rh/xantphos catalyst system in a two-stage hydroformylation-reductive amidation using pure 4-PA as feedstock. The use of 3-PA as a substrate not only results in a significantly lower regioselectivity for the 7-membered lactam, but also in the formation of high amounts of valeramide (VA). Consequently, a best overall yield of caprolactam of nearly 40% could be demonstrated with a Rh/POP-xantphos [POP-xantphos=4,5-bis(2,8-dimethyl-10-phenoxaphosphino)-9,9,-dimethylxanthene] catalyst system based on the 3:1 mixture of 3-PA/4-PA directly obtainable from GVL., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Different factors have been reported to influence islet isolation outcome, but their importance varies between studies and are hampered by the small sample sizes in most studies. The purpose of this study was to perform a systematic review to assess the impact of donor-, pancreas-, and isolation-related variables on successful human islet isolation outcome. PubMed, Embase, and Web of Science were searched electronically in April 2009. All studies reporting on donor-, pancreas-, and isolation-related factors relating to prepurification and postpurification islet isolation yield and proportion of successful islet isolations were selected. Seventy-four retrospective studies had sufficient data and were included in the analyses. Higher pre- and postpurification islet yields and a higher proportion of successful islet isolations were obtained when pancreata were preserved with the two-layer method rather than University of Wisconsin solution in donors with shorter cold ischemia times (CITs) [1 h longer CIT resulted in an average decline of prepurification and postpurification yields and proportion of successful isolations of 59 islet equivalents (IEQs)/g, 54 IEQs/g, and 21%, respectively]. Higher prepurification yields and higher percentage of successful islet isolations were found in younger donors with higher body mass index. Lower yields were found in donation after brain death donors compared to donation after cardiac death donors. Higher postpurification yields were found for isolation with Serva collagenase. This review identified donor-, pancreas-, and isolation-related factors that influence islet isolation yield. Standardized reports of these factors in all future studies may improve the power and identify additional factors and thereby contribute to improving islet isolation yield.

Cu(I)(Py2NS) (1) is formed by addition of Cu(I) to a solution of the pyridyl-thiol ligand N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine (Py2NSH). Oxidation of complex 1 by air leads to the formation of Cu(II) sulfinate and Cu(II) sulfonate complexes, providing a model for the oxidative degeneration of copper-sulfur enzymes. Crystal structures were obtained for two Cu(II) sulfinate complexes, [Cu(II)2(Py2NSO2)2](BF4)2·2(CH3)2CO (4a) and [Cu(II)2(Py2NSO2)2(OTf)2] (4b), which were further characterized by UV-vis and EPR spectroscopy and cyclic voltammetry. Furthermore, two Cu(II) sulfonate complexes with the proposed formulas Cu(II)2(Py2NSO3)2(BF4)2 (5a) and Cu(II)2(Py2NSO3)2(OTf)2 (5b) have been isolated and characterized. Monitoring the oxidation of 1 by UV-vis indicates that the oxidation proceeds via a dinuclear Cu(II) μ-thiolate complex (3); as an intermediate an octanuclear mixed-valent Cu(I)4Cu(II)4 cluster with formula [Cu(I)4Cu(II)4(Py2NS)4(μ-OH)2(CH3CN)6](ClO4)6·2CH3CN (2) was isolated and characterized by X-ray single crystal structure determination.

A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HOR(F) ) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80% selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HOR(F) , the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HOR(F) , in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work the thermal and photochemical reactivity of a series of ruthenium complexes [Ru(terpy)(N-N)(L)](X)2 (terpy = 2,2';6',2″-terpyridine, L = 2-(methylthio)ethanol (Hmte) or water, and X is Cl(-) or PF6(-)) with four different bidentate chelates N-N = bpy (2,2'-bipyridine), biq (2,2'-biquinoline), dcbpy (6,6'-dichloro-2,2'-bipyridine), or dmbpy (6,6'-dimethyl-2,2'-bipyridine), is described. For each chelate N-N the thermodynamic constant of the dark equilibrium between the aqua- and Hmte- complexes, the Hmte photosubstitution quantum yield, and the rate constants of the thermal interconversion between the aqua and Hmte complexes were measured at room temperature. By changing the steric hindrance and electronic properties of the spectator N-N ligand along the series bpy, biq, dcbpy, dmbpy the dark reactivity clearly shifts from a nonlabile equilibrium with N-N = bpy to a very labile thermal equilibrium with N-N = dmbpy. According to variable-temperature rate constant measurements in the dark near pH = 7 the activation enthalpies for the thermal substitution of H2O by Hmte are comparable for all ruthenium complexes, whereas the activation entropies are negative for bpy and biq, and positive for dcbpy and dmbpy complexes. These data are indicative of a change in the substitution mechanism, being interchange associative with nonhindered or poorly hindered chelates (bpy, biq), and interchange dissociative for more bulky ligands (dcbpy, dmbpy). For the most labile dmbpy system, the thermal equilibrium is too fast to allow significant modification of the composition of the mixture using light, and for the nonhindered bpy complex the photosubstitution of Hmte by H2O is possible but thermal binding of Hmte to the aqua complex does not occur at room temperature. By contrast, with N-N = biq or dcbpy the thermodynamic and kinetic parameters describing the formation and breakage of the Ru-S bond lie in a range where the bond forms spontaneously in the dark, but is efficiently cleaved under light irradiation. Thus, the ratio between the aqua and Hmte complex in solution can be efficiently controlled at room temperature using visible light irradiation.

A systematic library of 24 nickel(II) complexes with bidentate diphosphane ligands was synthesized, and the solid-state structures of five of them were determined with X-ray crystallography. The compounds C1-C3 are common P2Ni(II)X2-type complexes, while C4 contains a unique [P2Ni(II)(NH3)(OAc)](+) square-planar structure with a P2NO donor set and C5 constitutes a rare [(P2Ni(II))2(μ-OH)2](2+) dinuclear compound. The catalytic activity of all complexes was tested in the hydrogenation and/or isomerization of 1-octene in a CH2Cl2/CH3OH reaction medium. Catalyst precursors bearing ligands with o-alkoxy aryl rings selectively hydrogentate 1-octene to n-octane, while catalytic systems comprising ligands without the o-alkoxy functionality selectively isomerize the substrate to a mixture of internal alkenes, mostly cis- and trans-2-octene. The conversion is enhanced by equipping the ligand aryl rings with electron-donating alkoxy groups, by increasing the steric bulk of the backbone and/or the aryl rings, by employing relatively noncoordinating anions, and by adding a base as the cocatalyst. Using the compound [Ni(L3X)I2] as the catalyst precursor and upon application of standard hydrogenation conditions, full conversion of the substrate was achieved in 1 h to isomerization products only (TON = 1940). When a catalytic amount of the base is added, a similar result is obtained even in the absence of H2. A maximum TON of 4500 in 1 h with 96% selectivity for n-octane was achieved by employing [Ni(oMeO-L3X)(NH3)(OAc)]PF6 as the catalyst precursor.

The reactivity of palladium complexes of bidentate diaryl phosphane ligands (P(2)) was studied in the reaction of nitrobenzene with CO in methanol. Careful analysis of the reaction mixtures revealed that, besides the frequently reported reduction products of nitrobenzene [methyl phenyl carbamate (MPC), N,N'-diphenylurea (DPU), aniline, azobenzene (Azo) and azoxybenzene (Azoxy)], large quantities of oxidation products of methanol were co-produced (dimethyl carbonate (DMC), dimethyl oxalate (DMO), methyl formate (MF), H(2)O, and CO). From these observations, it is concluded that several catalytic processes operate simultaneously, and are coupled via common catalytic intermediates. Starting from a P(2)Pd(0) compound formed in situ, oxidation to a palladium imido compound P(2)Pd(II)=NPh, can be achieved by de-oxygenation of nitrobenzene 1) with two molecules of CO, 2) with two molecules of CO and the acidic protons of two methanol molecules, or 3) with all four hydrogen atoms of one methanol molecule. Reduction of P(2)Pd(II)=NPh to P(2)Pd(0) makes the overall process catalytic, while at the same time forming Azo(xy), MPC, DPU and aniline. It is proposed that the Pd-imido species is the central key intermediate that can link together all reduction products of nitrobenzene and all oxidation products of methanol in one unified mechanistic scheme. The relative occurrence of the various catalytic processes is shown to be dependent on the characteristics of the catalysts, as imposed by the ligand structure., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

When studying histological characteristics of porcine pancreata in relation to islet isolation, a remarkably high number of hyperemic islets (HIs) was encountered. The abnormalities observed in these HIs ranged from a single dilated vessel to hemorrhages extending into the surrounding exocrine tissue. The aim of the present study was to compare pancreata with and without HI on islet isolation outcomes. This study involved a histological examination of 143 purebred (74 juvenile and 69 adult) and 47 crossbred (only juvenile) porcine pancreata. Islet isolation was performed in 48 purebred adult pigs and in 25 crossbred pigs. Tissue samples were stained with Aldehyde Fuchsine. The presence of HIs was scored semi-quantitatively (HI-, HI+). We observed HIs in 48% of the purebred and in 68% of the crossbred pigs. However, only 3.3±3.1% and 3.1±4.7% of all assessed islets was hyperemic in HI+ pancreata in purebred and crossbred pigs, respectively. In both groups, significantly higher endocrine cell mass was found in the HI+ pancreata (p<0.01). When the higher endocrine cell mass was taken into account, we found significantly lower yields in the HI+ pancreata in both purebred and crossbred pigs (p=0.03 in both groups). The presence of HIs occurs frequently in porcine donor-pancreata and is associated with reduced isolation outcomes., (Georg Thieme Verlag KG Stuttgart · New York.)

When studying histological characteristics of human donor-pancreata, a remarkably high number of hyperemic islets (HIs) were encountered. The abnormalities in these HIs ranged from single/multiple dilated vessels to hemorrhages extending into the exocrine tissue. We aimed to determine the relevance of the presence of HIs in human donor-pancreata for isolation outcome and to identify donor and procurement factors associated with the occurrence of HIs. The presence of HIs was scored semi-quantitatively (HI-, HI+) in 102 human donor-pancreata. Islet isolation was performed in 40 cases. Donor and procurement factors were retrospectively analyzed in 94 donors. HIs were found in 54.6% of all donor-pancreata. However, only 4.5% of all islets in the affected pancreata was hyperemic. The affected pancreata contained slightly more endocrine tissue, but produced significantly lower yields. When corrected for other factors known to influence isolation outcome, the presence of HIs and endocrine content were the only factors significantly influencing isolation outcome. Prolonged ICU stay and pre-procurement hypertension were associated with the presence of HIs. This study is a first indication that the presence of HIs in human donor-pancreata are associated with reduced isolation outcomes and suggest an impact of the procurement procedure and pre-procurement hemodynamic status of the donor on the islet quality. It is tempting to speculate that this contributes to the generally experienced difficulties in obtaining sufficient amounts of human islets., (© Georg Thieme Verlag KG Stuttgart · New York.)

Complexes of the type [Pd(ligand)(2)](anion)(2) were prepared with a series of bidentate di(o-methoxyphenyl)phosphine ligands with increasing steric bulk on the meta position of the phenyl groups: m-H (L1); m-MeO (L2); and m-Me (L3). The solid-state structure of [Pd(L2)(2)](OTs)(2) revealed that the two ligands are symmetrically coordinated to Pd(2+). In the solid state structure of [Pd(L3)(2)](OTs)(2) however, the two ligands are unsymmetrically coordinated to Pd(2+), yielding an unprecedented conformation of this bis-chelate P(4)Pd(2+) complex. (1)H-(1)H-COSY and NOESY analysis and a (31)P-NMR simulation showed that the asymmetric structure of [Pd(L3)(2)](OTs)(2) is retained in solution.

Background: A remarkable change in porcine islet morphology was observed after infusion of the pancreas with collagenase. The aim of the present study was to quantify these morphological changes and to assess whether these changes were due to the volume expansion caused by the collagenase entering the islet or the result of its digestive effects., Methods: This study was performed in pancreata of 28 crossbred pigs. First, eight pancreata were intraductally injected with collagenase by a continuous controlled pressure of 180 mmHg. Pancreas samples before collagenase infusion were used as controls. All tissue samples, both before and after infusion, were stained with anti-insulin. To quantify the morphological change of the islets, the mean beta cell/endocrine content ratio of the infused and not-infused tissue samples was compared. In a second experiment, 20 pancreata were similarly assessed after intraductal injection with Hank's balanced salt solution (HBSS)., Results: In both the collagenase- and HBSS-infused groups, mean beta cell/endocrine content ratio was lower than in the control samples. The observed decline in the beta cell/endocrine content ratio was not significantly different between collagenase- and HBSS-infused pancreata. This suggests that the lower beta cell/endocrine content ratio and thus the morphological change in the infused tissue samples is caused by volume expansion of the fluid entering the islet and that the digestive effect of collagenase plays no or only a minor role., Conclusion: Morphological changes of islets are observed after infusion of pancreata with collagenase and HBSS, most likely caused by volume expansion due to fluid entering the islets., (© 2010 John Wiley & Sons A/S.)

Variable islet yields in porcine islet isolation may be caused by the collagen substrate within the pancreas. The aim of the present study was to determine the total amount and distribution of collagen within porcine pancreata and their relationship to islet isolation outcome. A total of 64 juvenile and 76 adult porcine pancreata of eight purebred breeds were histologically examined. The amount of collagen was quantitatively assessed in tissue samples stained with Sirius Red. Collagen distribution was semi-quantitatively determined by assessing the presence of collagen in the endocrine-exocrine interface and within the islet, in tissue samples stained with Sirius Red and anti-insulin. Islet isolation was performed in 58 pancreata of the adult group. Total collagen content and islet encapsulation ranged widely in both adult and juvenile pigs. However, the majority of islets in adult and juvenile pigs had no or only a limited collagen capsule. The difference in collagen content between adult and juvenile pigs could not be explained by age. Furthermore, no differences between adult and juvenile pigs were found in islet encapsulation or the amount of intra-islet collagen. In adult pigs, no significant relationships were found between obtained islet yield and total collagen content, islet encapsulation or amount of collagen within the islet. Considering the limitations in experimental design (staining method) and study material, isolation outcome does not seem to be affected by the total collagen content or collagen distribution. The influence of other matrix elements and collagen subtypes should be investigated.

Global warming concern has dramatically increased interest in using CO2 as a feedstock for preparation of value-added compounds, thereby helping to reduce its atmospheric concentration. Here, we describe a dinuclear copper(I) complex that is oxidized in air by CO2 rather than O2; the product is a tetranuclear copper(II) complex containing two bridging CO2-derived oxalate groups. Treatment of the copper(II) oxalate complex in acetonitrile with a soluble lithium salt results in quantitative precipitation of lithium oxalate. The copper(II) complex can then be nearly quantitatively electrochemically reduced at a relatively accessible potential, regenerating the initial dinuclear copper(I) compound. Preliminary results demonstrate six turnovers (producing 12 equivalents of oxalate) during 7 hours of catalysis at an applied potential of -0.03 volts versus the normal hydrogen electrode.

To evaluate whether further improvement in porcine islet xenotransplantation is feasible, a number of questions were addressed. Earlier we showed significant improvement in the nude mouse of the porcine islets by selection through long-term culture. Now these islets were tested in the stringent pig-to-rat model. Islets were isolated from adult pigs, cultured for 1.5-3 weeks and transplanted to rats. Possible rejection mechanisms were assessed by interference of the cellular response with cyclosporine A (CsA), blocking macrophages with gadolinium chloride (GdCl), and suppressing the humoral response with cyclophosphamide. Modifications in graft size and condition were analyzed. Untreated control recipients showed primary nonfunction (PNF). CsA treatment could fully overcome PNF and resulted in graft survival from 10 to over 134 days. Rejection was the main cause of function loss. Although rejection could not be prevented by intensifying the induction therapy, increased maintenance immunosuppression effectively blocked rejection, albeit at the expense of toxicity. Blocking the humoral response was ineffective; all grafts showed PNF. In contrast, depletion of macrophages fully prevented PNF. Combination of GdCl and CsA gave no additional effect, and grafts were rejected between 57 and 162 days. Generally, graft survivals were similar to those reported in the literature; however, long-term cultured islets required much less maintenance immunosuppression. Cessation of graft function was not always due to rejection; in some cases "islet exhaustion" was found, possibly caused by discrepancy between the graft size and the rapidly growing recipient. Neither the presence of damaged islet tissue in the graft nor the size of the graft exerted any influence on graft survival. On rejection, no real infiltration of the graft was seen; destruction gradually processed from the outside. The good functional capability of the cultured islets was illustrated by disappearance of the clinical symptoms and increase in body weight, which almost doubled in the long-term survivors.

Tris(o-anisyl)phosphane was reacted with ruthenium(III) chloride forming a novel Ru(III) complex of formula [Ru(PAn(3))(P(An)(phenolate)(2))Cl] containing a tridentate dianionic P,O,O-ligand and a bidentate neutral P,O ligand. The tridentate ligand was formed by elimination of two methyl groups from the starting ligand in the reaction with the ruthenium salt. The molecular structure was determined by single crystal X-ray diffraction analysis. The compound shows a high cytotoxic activity in ovarian cancer cell lines comparable with cisplatin and overcoming cisplatin-resistance.