Parental decision making about safer sleep practices: A qualitative study of the perspectives of families with additional health and social care needs.

INTRODUCTION: Despite a decline in Sudden Unexpected Death in Infancy in the UK since 2004, inequalities have widened with higher rates among families from deprived backgrounds and those known to child protection services. Almost all cases involve parents who had engaged in unsafe sleeping practices despite awareness of safer sleeping advice. OBJECTIVE: To understand the perspectives surrounding safer sleep of families supported by statutory child protection agencies, and use behavior change theory to inform how approaches to providing safer sleep advice to these families may be modified. PARTICIPANTS AND SETTING: We interviewed 14 mothers, 2 fathers and one grandmother, who had recent contact with child protection services in northeast England. METHODS: In-depth, semi-structured interviews, with purposive sampling. The COM-B model (Capability, Opportunity, and Motivation) structured our analysis. RESULTS: Parents described how anxiety, sleep deprivation, settling infants, illness, and a desire to bond with infants influence their decision making about sleep. Parents valued credible, trusted sources and understanding how safer sleep practices protect infants. Responses to questions about 'out of routine' situations suggested social pressures surrounding routines and 'good parenting' may preclude parents from acknowledging risks and planning for these situations. CONCLUSION: Open conversations tailored to the needs of families, focused upon understanding why and when parent(s) do or do not follow safer sleep guidance seem a promising way of promoting safer sleep practices. Safer sleep discussions with these families are likely to be best delivered as part of wider infant care by professionals who have an established and continuing trusting relationship with parents. While advice and information should be provided by any professional in contact with the family with the necessary expertise, sensitive conversations around sleeping practices, particularly co-sleeping, may be more easily facilitated by professionals where the statutory responsibility for safeguarding is less apparent.

"They had clothes on their back and they had food in their stomach, but they didn't have me": The contribution of parental mental health problems, substance use, and domestic violence and abuse on young people and parents.

BACKGROUND: The parental risk factors of mental health problems, substance use, and domestic violence and abuse each individually negatively impacts children's health and developmental outcomes. Few studies have considered the lived experience and support needs of parents and children in the real-world situation where these common risks cluster. OBJECTIVE: This study explores parents' and young people's lived experiences of the clustering of parental mental health problems, parental substance use, and domestic violence and abuse. METHODS: Semi-structured interviews were conducted with 18 mothers, 6 fathers, and 7 young people with experiences of these parental risk factors. Transcribed interviews were analysed using reflexive thematic analysis. RESULTS: Four themes were developed, 1) cumulative adversity, 2) the impact of syndemic risk, 3) families navigating risk, and 4) family support. Parents and young people described family situations of stress wherein they experienced cumulative impact of multiple parental risk factors. Parents sought to navigate stressors and parent in positive ways under challenging conditions, often impeded by their own childhood trauma and diminished confidence. Parents and young people spoke of the need for, and benefits of having, support; both as a family and as individuals, to successfully address this trio of parental risks and the related impact. CONCLUSIONS: This study highlights the high level of stress families experience and the efforts they go to mitigate risk. Services and interventions need to reflect the complexity of multiple needs and consider both the whole family and individuals when providing support.

Interventions to Reduce Parental Substance Use, Domestic Violence and Mental Health Problems, and Their Impacts Upon Children's Well-Being: A Systematic Review of Reviews and Evidence Mapping.

INTRODUCTION: Children exposed to parental intimate partner violence and abuse, mental illness, and substance use experience a range of problems which may persist into adulthood. These risks often co-occur and interact with structural factors such as poverty. Despite increasing evidence, it remains unclear how best to improve outcomes for children and families experiencing these adversities and address the complex issues they face. AIMS AND METHODS: Systematic review of systematic reviews. We searched international literature databases for systematic reviews, from inception to 2021, to provide an evidence overview of the range and effectiveness of interventions to support children and families where these parental risk factors had been identified. RESULTS: Sixty-two systematic reviews were included. The majority (n = 59) focused on interventions designed to address single risk factors. Reviews mostly focused on parental mental health (n = 38) and included psychological interventions or parenting-training for mothers. Only two reviews assessed interventions to address all three risk factors in combination and assessed structural interventions. Evidence indicates that families affected by parental mental health problems may be best served by integrated interventions combining therapeutic interventions for parents with parent skills training. Upstream interventions such as income supplementation and welfare reform were demonstrated to reduce the impacts of family adversity. CONCLUSION: Most intervention approaches focus on mitigating individual psychological harms and seek to address risk factors in isolation, which presents potentially significant gaps in intervention evidence. These interventions may not address the cumulative impacts of co-occurring risks, or social factors that may compound adversities.

Effectiveness of wound contact layers in enabling undisturbed wound management: a case series.

OBJECTIVE: Wound contact layers (WCLs) are intended to protect and support wounds during the healing process. An open, non comparative, case series clinical evaluation was undertaken to assess the impact of these dressings on establishing an undisturbed wound environment that supports effective wound management, and to allow the establishment of limits of duration of the wear time for the experimental WCLs. METHOD: The primary objectives of this clinical evaluation were to assess the ability of the WCLs to prevent tissue disturbance to the wound and surrounding skin and for the clinicians to have confidence to extend the wear time of the WCL dressings. For them to have confidence in leaving the dressings in place for extended periods, the assessment of the wound and periwound skin condition and an assessment of patient comfort was performed: assessment of wound and periwound condition in relation to tissue adherence of the dressing to the wound resulting in tissue damage/bleeding (to wound and/or periwound skin) and cellular infiltration into the WCL; assessment of patient wearing comfort and satisfaction; assessment of WCL wear time, relating to times between dressing changes as judged by the clinician. RESULTS: Based upon five parameters used to assess the extent to which the WCLs Atrauman, Atrauman Silicone and Atrauman Ag (HARTMANN, Germany) disturbed the underlying tissues-bleeding, wound tissue damage, periwound skin damage, tissue ingrowth and dressing adherence-the majority (>95%) of assessments indicated low or no disturbance of tissue. Over the 14 days of study assessment, the mean (±standard deviation) wear time was 7.3±1.2 days for the Atrauman group, 9.9±2.8 days for the Atrauman Silicone group, and 5.8±1.0 days for the Atrauman Ag group. All dressings were well tolerated by patients and rated highly in terms of in-use dressing performance. CONCLUSION: The results indicate that Atrauman WCLs are suitable for the management of a variety of wounds as they promote an undisturbed wound environment, including extended wear time.

Impact of the COVID-19 pandemic on expectant and new parents' experience of pregnancy, childbirth, breast feeding, parental responsiveness and sensitivity, and bonding and attunement in high-income countries: a systematic review of the evidence.

OBJECTIVES: To review the evidence on how pregnancy, birth experience, breast feeding, parental responsiveness and sensitivity, and bonding and attunement were impacted by COVID-19. METHODS: We searched eight literature databases and websites of relevant UK-based organisations. The review focused on evidence during pregnancy and the early years (0-5 years). Studies of any study design published in English from 1 March 2020 to 15 March 2021 and conducted in high-income countries were included. Screening and data extraction were undertaken in duplicate. Evidence was synthesised using a narrative approach. Study quality of included studies was assessed using the Mixed Methods Appraisal Tool. RESULTS: The search yielded 9776 publications, of which 26 met our inclusion criteria. Significant knowledge gaps on how COVID-19 affected pregnancy and breast feeding limited healthcare providers' ability to provide consistent evidence-based information and care at the start of the pandemic. There was an enduring sense of loss about loved ones being restricted from taking part in key moments. Parents were concerned about the limitations of virtual healthcare provision. Some parents reported more opportunities for responsive breast feeding and improved parent-infant bonding due to reduced social and work pressures. Women from minoritised ethnic groups were less likely to continue breast feeding and attributed this to a lack of face-to-face support. CONCLUSIONS: The evidence suggests that new and expectant families have been both negatively and positively impacted by the COVID-19 pandemic and the resulting restrictions. The impacts on parents' opportunities to bond with their young children and to be attuned to their needs were felt unequally. It is important that emergency response policies consider the mother and the partner as a family unit when making changes to the delivery of maternal and child health and care services, so as to mitigate the impact on the family and existing health inequalities. PROSPERO REGISTRATION NUMBER: CRD42021236769.

Parental intimate partner violence and abuse during the COVID-19 pandemic: Learning from remote and hybrid working to influence future support.

OBJECTIVES: The COVID-19 pandemic has exacerbated intimate partner violence and abuse. Incidents of intimate partner violence and abuse have increased as a result of household tensions due to enforced coexistence (multiple national lockdowns and working from home practices), economic stress related to loss of income, the disruption of social and protective networks and the decreased access to support services. This study aimed to understand how female survivors of parental intimate partner violence and abuse have experienced the adapted multi-agency response to intimate partner violence and abuse during the pandemic and consider learning from remote and hybrid working to influence future support. METHOD: This study adopted a qualitative research design, utilizing semi-structured interviews and a focus group. Data collection took place between March and September 2021. In total, 17 female survivors of intimate partner violence and abuse took part in the project; we conducted the semi-structured interviews via telephone (n = 9) and conducted an online focus group (n = 8). RESULTS: Findings identified that services for those experiencing intimate partner violence and abuse need to be innovative, flexible and adaptable and 'reach out' to survivors rather than waiting for survivors to 'reach in' and ask for support. Findings show that the digital space highlights 'missed opportunities' for engagement with both professionals and peers and the potential for digital poverty is a key implication, which risks entrenching existing inequalities. CONCLUSION: In-depth consideration needs to be given to the design, delivery and evaluation of online interventions and provision of support to improve access and acceptability of services, maximize their effectiveness and to support the safety of survivors.

Challenges and Approaches to Green Social Prescribing During and in the Aftermath of COVID-19: A Qualitative Study.

The last decade has seen a surge of interest and investment in green social prescribing, however, both healthcare and social enterprise has been impacted by the COVID-19 crisis, along with restricted access to public green spaces. This study examines the challenges and opportunities of delivering green social prescribing during and in the aftermath of COVID-19, in the light of goals of green social prescribing to improve mental health outcomes and reduce health inequalities. Thirty-five one-to-one interviews were conducted between March 2020 and January 2022. Interviewees included Link Workers and other social prescribers, general practitioners (GPs), managers, researchers, and volunteers working in urban and rural Scotland and North East England. Interview transcripts were analyzed in stages, with an inductive approach to coding supported by NVivo. Findings revealed a complex social prescribing landscape, with schemes funded, structured, and delivered diversely. Stakeholders were in general agreement about the benefits of nature-based interventions, and GPs and volunteers pointed out numerous benefits to participating in schemes such as parkrun. Link Workers were more circumspect about suggesting outdoor activities, pointing out both psychological and practical obstacles, including health anxieties, mobility issues, and transport deficits. Exacerbated by the pandemic, there was a way to go before older and/multi-morbidity clients (their largest cohort) would feel comfortable and safe to socialize in open air spaces. Our findings support the premise that time spent in open green spaces can alleviate some of the negative mental health effects compounded by the pandemic. However, the creation of healthy environments is complex with population health intrinsically related to socioeconomic conditions. Social disadvantage, chronic ill health and health crises all limit easy access to green and blue spaces, while those in the most socially economically deprived areas receive the lowest quality of healthcare. Such health inequities need to be borne in mind in the planning of schemes and claims around the potential of future nature-based interventions to reduce health inequalities.

Sexual harassment in secondary school: Prevalence and ambiguities. A mixed methods study in Scottish schools.

BACKGROUND: Adolescence is characterized by identity formation, exploration and initiation of intimate relationships. Much of this occurs at school, making schools key sites of sexual harassment. Schools often lack awareness and understanding of the issue, and UK research on the topic is scarce. We explored prevalence and perceptions of sexual harassment in a school-based mixed-methods study of 13-17 year-old Scottish adolescents. METHODS: A student survey (N = 638) assessed past 3-months school-based victimization and perpetration prevalence via 17 behavioral items based on the most commonly used school-based sexual harassment measure ('Hostile Hallways'). Eighteen focus groups (N = 119 students) explored which of 10 behaviors were perceived as harassing/unacceptable and why. RESULTS: Two-thirds reported any victimization: 64.7% 'visual/verbal' (e.g. sexual jokes) and 34.3% 'contact/personally-invasive' behaviors (e.g. sexual touching; most of whom also reported experiencing visual/verbal types) in the past 3-months. Data suggested a gateway effect, such that contact/personally-invasive behaviors are more likely to be reported by those also reporting more common visual/verbal behaviors. Some survey participants reported being unsure about whether they had experienced certain behaviors; and in focus groups, participants expressed uncertainty regarding the acceptability of most behaviors. Ambiguities centered on behavioral context and enactment including: degree of pressure, persistence and physicality; degree of familiarity between the instigator-recipient; and perception of the instigator's intent. In attempting to resolve ambiguities, students applied normative schemas underpinned by rights (to dignity, respect and equality) and 'knowingness', usually engendered by friendship. CONCLUSIONS: Our study confirms school-based sexual harassment is common but also finds significant nuance in the ways in which students distinguish between acceptable and harassing. School-based strategies to tackle sexual harassment must engage with this complexity.

Weathering the storm: A qualitative study of social prescribing in urban and rural Scotland during the COVID-19 pandemic.

OBJECTIVES: The non-clinical approach known as social prescribing aims to tackle multi-morbidity, reduce general practitioner (GP) workload and promote wellbeing by directing patients to community services. Usual in-person modes of delivery of social prescribing have been virtually impossible under social distancing rules. This study qualitatively examined and compared the responses of three social prescribing schemes in Scotland to the COVID-19 pandemic. METHODS: We interviewed a theoretical sample of 23 stakeholders in urban and rural social prescribing schemes at the start of COVID-19 pandemic. Follow-up interviews with a representative sample were conducted around 10 months later. Interviewees included social prescribing coordinators (SPCs) GPs, managers, researchers and representatives of third sector organizations. Interview transcripts were analysed in stages and an inductive approach to coding was supported by NVivo. RESULTS: Findings revealed a complex social prescribing landscape in Scotland with schemes funded, structured and delivering services in diverse ways. Across all schemes, working effectively during the pandemic and shifting to online delivery had been challenging and demanding; however, their priorities in response to the pandemic had differed. With GP time and services stretched to limits, GP practice-attached 'Link Workers' had taken on counselling and advocacy roles, sometimes for serious mental health cases. Community-based SPCs had mostly assumed a health education role, and those on the Western Isles of Scotland a digital support role. In both rural or urban areas, combatting loneliness and isolation - especially given social distancing - remained a pivotal aspect of the SPC role. CONCLUSION: This study highlights significant challenges and shifts in focus in social prescribing in response to the pandemic. The use of multiple digital technologies has assumed a central role in social prescribing, and this situation seems likely to remain. With statutory and non-statutory services stretched to their limits, there is a danger of SPCs assuming new tasks without adequate training or support.

Clinical evaluation of a superabsorbent polymer dressing in enabling self-care of wounds.

Patient involvement in their own treatment can enable those with wounds in the community to play an active role in the management of their condition by, for example, completing dressing changes between health professional visits. The original primary study was undertaken to assess the clinical effectiveness of Zetuvit Plus Silicone Border (ZPSB) on exudate management. This retrospective sub-group analysis is aimed to demonstrate the effectiveness of a superabsorbent polymer (SAP) dressing (ZPSB) in enabling patients or their carers to undertake unsupervised dressing changes on their own. ZPSB was found to be clinically effective in this subgroup of patients, while also having additional features that enabled the patient to self-care. Overall, ZPSB enabled the patient to be part of their treatment plan and play an active role in the care of their wounds, thereby promoting self-care. This had a positive effect on nursing time saving and patient satisfaction.

Treatment of 52 patients with a self-adhesive siliconised superabsorbent dressing: a multicentre observational study.

OBJECTIVE: To provide 'in use' clinical data to support exudate management in patients with moderately to highly exuding wounds with bordered superabsorbent wound dressing with a silicone adhesive interface. METHOD: This study was an open-labelled non-comparative study. Patients included in the study were selected by the clinical investigator(s) according to whether the patient required a dressing for the management of moderately to highly exuding wounds. RESULTS: The primary aim of this study was to evaluate the clinical objective in relation to exudate handling (moderate to high) with a superabsorbent silicone border dressing (Zetuvit Plus Silicone Border; SAP silicone border dressing; designated RespoSorb Silicone Border in some countries). The SAP border dressing had met the clinical objectives relating to exudate management, affirmed by the health professionals with a yes response in 94% of cases. Additionally, the health professionals rated the handling of exudate as excellent/good (78%) and most (80%) reported that they would use the SAP silicone border dressing again. Allied to this was the fact that the SAP silicone border dressing improved the wound edge and periwound skin conditions (29% and 36% of patients, respectively). Regarding dressing retention, the SAP silicone border dressing retained its position in 72% of patients. For wear time, the largest proportion of dressing changes, both pre-study and during the evaluation period, was every third day (45% and 44%, respectively). But there was a shift to extended wear time with use of the SAP silicone border dressing with 72% of patients' dressing changes being every third day or longer. CONCLUSION: The SAP silicone border dressing was successful in managing wound exudate in moderately to highly exuding wounds and consequently this had a beneficial impact on the wound edge and periwound skin. Overall, there was a positive effect on wound bed preparation and in turn the healing response was progressive. This study has shown that the SAP silicone border dressing successfully controlled exudate and provided positive benefits when used in the treatment of patients with moderately to highly exuding wounds.

Evaluation of a superabsorbent wound dressing, patient and clinician perspective: a case series.

OBJECTIVE: The primary objective of this study was to evaluate the fluid management capabilities of a superabsorbent wound dressing (Zetuvit Plus Silicone), with secondary objectives related to parameters that support whether the dressing enables undisturbed healing. METHOD: This study was an open labelled non-comparative study. Patients included in the study were selected by the clinical investigator(s) according to whether the patient required a dressing for the management of moderately to highly exuding wounds. RESULTS: A total of 50 patients were included in the study. Results related to the primary objective demonstrated that the superabsorbent wound dressing was able to absorb all levels of exudate across the range (low to high). At each assessment time point these results show that in 98% of assessments the superabsorbent dressing was rated as 'very good' (91%) or 'good' (7%) at exudate management. Secondary objectives relating to wound bed preparation, healing and management of pain were also positive. Additionally, at the end of each patient treatment, the dressing's fluid management capabilities were rated overall as 'excellent' (100% of cases). There was little pain associated with the wound or at dressing change throughout the study and its flexibility/conformability allowed for comfort and patient satisfaction aligned with increased quality of life. Additionally, inclusion of a silicone adhesive layer allowed painless and atraumatic removal of the dressing, increasing patient comfort, both during wear and at dressing removal, and supported the description of enabling undisturbed wound healing. CONCLUSION: The superabsorbent wound dressing achieved the primary objective relating to wound exudate management in all the assessments undertaken in this study. In addition, the silicone interface allowed for undisturbed healing as evidenced by little or no adherence of the dressing to underlying tissue, preventing damage to periwound skin. Overall, the superabsorbent wound dressing with the addition of the silicone interface could offer advantages over other superabsorbent polymer dressings (that might adhere to the wound surface) or silicone wound dressings (that might not have the absorbent properties of this type of dressing).

Virtual eye region: development of a realistic model to convey emotion.

The human eyes and their surrounding features are capable of conveying an array of emotional and social information through expressions. Producing virtual human eyes which are able to communicate these complex mental states continues to be a challenging research topic in computer graphics (CG) as subtle inaccuracies can be the difference between realistic and uncanny. With the recent emergence of virtual customer service agents, the demand for expressive virtual eyes is increasing. One essential question that remains to be answered is: Can virtual human eyes effectively transmit emotion? Through a combination of 3D scanning and manual hand modelling techniques, we developed an efficient pipeline to realise a virtual model of the human eye area that displays real-world characteristics. From this model eye expression renders of the six basic emotions, anger, disgust, fear, happiness, sadness and surprise were generated (Ekman et al., 1969). The perceptual quality of the model was evaluated by showing respondents from two age groups the six eye expressions renders and corresponding real-world photos. Respondents then judged which of the six emotions best described each image. Our findings indicate a clear relationship between the recognition levels for both photographic and virtual stimuli plus a significant level of emotional perception was found for the virtual eye expressions of sadness and anger. This research of human cognition and CG is a starting point for investigating the use of artificial human eye expressions as an effective research tool in the perceptual community.

An observational study of a superabsorbent polymer dressing evaluated by clinicians and patients.

OBJECTIVE: This open, non-comparative, multi-centre investigation examines the use of a new superabsorbent polymer (SAP) wound dressing used for exudate management (in medium-to-high exuding wounds) in a patient population with a variety of wound types. The primary objective of this study was to evaluate the fluid management capabilities of the dressing. METHOD: Both acute and chronic wounds with moderate-to-high exudate production levels were assessed (over a period of two weeks) as requiring exudate management, with a SAP dressing, Zetuvit Plus (designated Resposorb Super in Europe), as part of their normal treatment regimen. Clinicians recorded a subjective assessment of exudate management and its impact on periwound skin conditions. In addition, wound bed preparation, healing trajectory and pain level reduction were monitored to give an insight into the clinical implications of using this dressing. Data was also collected from clinicians and patients on clinical performance of the dressing. RESULTS: The SAP dressing achieved ratings of 'very good'/'good' (83% and 13%, respectively) in relation to its wound exudate handling properties. The dressing supported improved wound healing, reduced damage to and enhanced the status of the periwound skin. Pain levels were reduced and, as a consequence, patient reported outcomes were improved. Patients commented that the exudate handling capabilities of the dressing, its conformability and comfort allowed them to resume a semblance of normality in their life. All participating clinicians indicated that they would continue to use the SAP dressing. A sub-population cost analysis has highlighted that, when compared to alternative (historical) exudate management treatments, the SAP dressing was less expensive. The cost reduction arises from data that shows product use and frequency of dressing change (that impacts on nurse time) are both reduced. For the 10 patients evaluated, total costs were £2,491 and £1,312 before and during use, respectively; a saving of £1,179.00 (47%). CONCLUSION: The SAP dressing was well tolerated and shown to be effective in the management of moderate-to-high exudate. Consequently, the dressing supported improved healing, and reduced damage to periwound skin, leading to lower pain levels. Overall, both the patients and clinicians rated the SAP highly.

Wound-bed preparation: a vital step in the healing process.

Non-healing wounds are a significant burden to healthcare systems, where it is estimated that 4-5% of the adult population has a problem wound at any one time ( Guest et al, 2017 ). It is suggested that infection is the most frequent complication in non-healing wounds where it can prolong patient treatment times and increase resource use ( Gottrup et al, 2013 ). Wound infection develops as a result of an imbalance between the patient's immune system and the conditions in the wound, which subsequently can promote bacterial proliferation ( Wounds UK, 2013 ). It can impact on the patient by delaying wound healing, increasing the risk of amputation and life-threatening conditions, and reducing quality of life. The use of antibiotics to treat wound infections has decreased due to the increased risk of antibiotic resistance ( Swanson et al, 2014 ). As a result alternative strategies for preventing and managing wound infection have been adopted, including wound debridement and the use of topical antiseptic/antimicrobial agents.

Spin States of Homochiral and Heterochiral Isomers of [Fe(PyBox)2 ]2+ Derivatives.

The following iron(II) complexes of 2,6-bis(oxazolinyl)pyridine (PyBox; LH ) derivatives are reported: [Fe(LH )2 ][ClO4 ]2 (1); [Fe((R)-LMe )2 ][ClO4 ]2 ((R)-2; LMe =2,6-bis{4-methyloxazolinyl}pyridine); [Fe((R)-LPh )2 ][ClO4 ]2 ((R)-3) and [Fe((R)-LPh )((S)-LPh )][ClO4 ]2 ((RS)-3; LPh =2,6-bis{4-phenyloxazolinyl}pyridine); and [Fe((R)-LiPr )2 ][ClO4 ]2 ((R)-4) and [Fe((R)-LiPr )((S)-LiPr )][ClO4 ]2 ((RS)-4; LiPr =2,6-bis{4-isopropyloxazolinyl}pyridine). Solid (R)-3⋅MeNO2 exhibits an unusual very gradual, but discontinuous thermal spin-crossover with an approximate T1/2 of 350 K. The discontinuity around 240 K lies well below T1/2 , and is unconnected to a crystallographic phase change occurring at 170 K. Rather, it can be correlated with a gradual ordering of the ligand conformation as the temperature is raised. The other solid compounds either exhibit spin-crossover above room temperature (1 and (RS)-3), or remain high-spin between 5-300 K [(R)-2, (R)-4 and (RS)-4]. Homochiral (R)-3 and (R)-4 exhibit more twisted ligand conformations and coordination geometries than their heterochiral isomers, which can be attributed to steric clashes between ligand substituents [(R)-3]; or, between the isopropyl substituents of one ligand and the backbone of the other ((R)-4). In solution, (RS)-3 retains its structural integrity but (RS)-4 undergoes significant racemization through ligand redistribution by 1 H NMR. (R)-4 and (RS)-4 remain high-spin in solution, whereas the other compounds all undergo spin-crossover equilibria. Importantly, T1/2 for (R)-3 (244 K) is 34 K lower than for (RS)-3 (278 K) in CD3 CN, which is the first demonstration of chiral discrimination between metal ion spin states in a molecular complex.

A Unified Treatment of the Relationship Between Ligand Substituents and Spin State in a Family of Iron(II) Complexes.

The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)2 ](2+) (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature (T1/2 ) in solution vs. the relevant Hammett parameter show that the low-spin state of the complex is stabilized by electron-withdrawing pyridyl ("X") substituents, but also by electron-donating pyrazolyl ("Y") substituents. Moreover, when a subset of complexes with halogeno X or Y substituents is considered, the two sets of compounds instead show identical trends of a small reduction in T1/2 for increasing substituent electronegativity. DFT calculations reproduce these disparate trends, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe-L σ and π bonding.

Iron(II) complexes of tridentate indazolylpyridine ligands: enhanced spin-crossover hysteresis and ligand-based fluorescence.

Reaction of 2,6-difluoropyridine with 2 equiv of indazole and NaH at room temperature affords a mixture of 2,6-bis(indazol-1-yl)pyridine (1-bip), 2-(indazol-1-yl)-6-(indazol-2-yl)pyridine (1,2-bip), and 2,6-bis(indazol-2-yl)pyridine (2-bip), which can be separated by solvent extraction. A two-step procedure using the same conditions also affords both 2-(indazol-1-yl)-6-(pyrazol-1-yl)pyridine (1-ipp) and 2-(indazol-2-yl)-6-(pyrazol-1-yl)pyridine (2-ipp). These are all annelated analogues of 2,6-di(pyrazol-1-yl)pyridine, an important ligand for spin-crossover complexes. Iron(II) complexes [Fe(1-bip)2](2+), [Fe(1,2-bip)2](2+), and [Fe(1-ipp)2](2+) are low-spin at room temperature, reflecting sterically imposed conformational rigidity of the 1-indazolyl ligands. In contrast, the 2-indazolyl complexes [Fe(2-bip)2](2+) and [Fe(2-ipp)2](2+) are high-spin in solution at room temperature, whereas salts of [Fe(2-bip)2](2+) exhibit thermal spin transitions in the solid state. Notably, [Fe(2-bip)2][BF4]2·2MeNO2 adopts a terpyridine embrace lattice structure and undergoes a spin transition near room temperature after annealing, resulting in thermal hysteresis that is wider than previously observed for this structure type (T1/2 = 266 K, ΔT = 16-20 K). This reflects enhanced mechanical coupling between the cations in the lattice through interdigitation of their ligand arms, which supports a previously proposed structure/function relationship for spin-crossover materials with this form of crystal packing. All of the compounds in this work exhibit blue fluorescence in solution under ambient conditions. In most cases, the ligand-based emission maxima are slightly red shifted upon complexation, but there is no detectable correlation between the emission maximum and the spin state of the iron centers.

Design, synthesis and binding studies of a novel quadruple ADDA hydrogen-bond array.

The design and synthesis of a novel ADDA hydrogen-bond array is described. The ureidodiimidazole motif (UDIM) 2 engages in interactions with complementary diamidonaphthyridine (DAN) 3 motifs with an association constant K(a) = 825 ± 16 M(-1) in chloroform. (1)H NMR and molecular modelling studies were carried out in order to explain the unexpected behaviour of this new supramolecular motif. These revealed that a combination of effects including; an energetic bias for the folded conformer, subtle differences in shape complementarity between the two components and the potential for self-association of UDIM 2 disfavour higher affinity interactions between the two components.

Mepitel One: a wound contact layer with Safetac technology.

This article examines the use of Mepitel One, a wound contact layer that promotes wound healing by using the clinical benefits of Safetac technology. A wide range of clinical evidence shows that dressings with Safetac prevent trauma, minimise wound pain and associated psychological stress, while facilitating undisturbed wound healing. Mepitel One has been developed as a highly transparent wound contact layer with Safetac on the wound contact surface alone; this makes it easy to apply without sticking to gloves, and allows it to be used with a choice of secondary dressings. The dressing can stay in place for up to 14 days and allows examination of the wound without removal. The clinical evidence reviewed here shows that Mepitel One is a versatile option for use on a wide range of wound types to promote undisturbed healing and minimise pain at dressing changes.