Applying the Crystalline Sponge Method to Agrochemicals: Obtaining X-ray Structures of the Fungicide Metalaxyl-M and Herbicide S-Metolachlor

The crystalline sponge method is a technique that provides the ability to elucidate the absolute structure of noncrystalline or hard to crystallize compounds through single-crystal X-ray diffraction by removing the need to obtain crystals of the target compound. In this study the crystalline sponges {[(ZnX_{2})_{3}(2,4,6-tris(4-pyridyl)-1,3,5-trazine)_{2}].x(solvent)}n (X = I, Br) were used to obtain X-ray structures of the agrochemical active ingredients metalaxyl-M and S-metolachlor. The effect of the temperature used during guest uptake and the influence of changing the host framework ZnX_{2} nodes on guest encapsulation were investigated. Additionally, three compounds containing chemical fragments similar to those of metalaxyl-M and S-metolachlor (phenylacetaldehyde, N-ethyl-o-toluidine, and methyl phenylacetate) were also encapsulated. This allowed for the effect of guest size on the position that guests occupy within the host frameworks to be examined. The disorder experienced by the guest compounds was documented, and an analysis of the intermolecular host–guest interactions (CH···π and π ···π) used for guest ordering within the host frameworks was also undertaken in this study

Police perceptions of problem-oriented policing and evidence-based policing: evidence from England and Wales

The history of policing is littered with reform programmes, which aim to improve effectiveness, efficiency and legitimacy. Problem-oriented policing (POP) and evidence-based policing (EBP) are two popular and enduring reform efforts, both of which have generated significant researcher and practitioner attention. There are important similarities between POP and EBP: both approaches provide a framework intended to improve the outcomes of policing. There are also key differences, however, in terms of their main objectives, standards of evidence and units of analysis. Despite both approaches being widely advocated and implemented, presently little is known about police practitioner understanding of the relationship between POP and EBP, both in principle and in practice. To address this gap, this paper draws on survey (n = 4,141) and interview (n = 86) data collected from 19 police forces in England and Wales in 2019 to explore police practitioners’ views on the relationship between POP and EBP, and the extent to which these two approaches inform contemporary police practices. Our findings indicate that respondents generally viewed the two approaches as complementary and important frameworks for orienting police work. However, respondents also drew attention to how the two approaches are not always connected organisationally nor in the minds of police personnel. In addition, challenges were identified in the application of both approaches in practice. Our results suggest that more needs to be done to maximise the potential of POP and EBP, both separately and synergistically. The article concludes by suggesting some ways in which this might be achieved

Antithrombotic drugs for cardiovascular risk reduction in patients with lower limb peripheral arterial disease: protocol for a systematic review and network meta-analysis of randomised controlled trials.

INTRODUCTION: The optimal antithrombotic regimen to reduce the risk of vascular events in patients with peripheral arterial disease (PAD) is contentious. This systematic review and network meta-analysis (NMA) aims to define the relative efficacy and risks of previously investigated antithrombotic medication regimens in preventing major cardiovascular events, vascular limb events and mortality in patients with PAD. METHODS AND ANALYSIS: A peer-reviewed, systematic search will be executed in English on Medline, Embase, Cochrane (CENTRAL), Web of Science and Google Scholar databases in late 2022. The WHO International Clinical Trials Registry platform will also be searched for ongoing trials. Abstracts will be screened independently by two researchers for randomised controlled trials meeting the review criteria. All associated publications including the study protocol will be sought and evaluated together against prespecified inclusion/exclusion criteria. Two researchers will extract the data into a prepiloted extraction form. Risk-of-bias assessments will be performed using the Cochrane 'Risk-of-Bias V.2' criteria by individuals with domain expertise. All differences will be resolved by consensus or a third individual for ties.Included trials will be summarised. An NMA will be performed, subject to checks of assumptions. Both primary and secondary outcomes will be analysed on a whole network basis. Pairwise comparisons and league tables will be produced. Prespecified subgroup analyses will include sex, ethnicity, disease status, conservative versus interventional management and key comorbidities. The findings will be evaluated using the Grading of Recommendation Assessment, Development and Evaluation, informed by patient and public involvement work. ETHICS AND DISSEMINATION: This is a systematic review of data in the public domain and does not require ethical approval. Dissemination will include presentations to key vascular and patient organisations, publication in a peer-reviewed journal and an open-access repository of the study data. PROSPERO REGISTRATION NUMBER: CRD42023389262

Protocol for the ROSE sustainment (ROSES) study, a sequential multiple assignment randomized trial to determine the minimum necessary intervention to maintain a postpartum depression prevention program in prenatal clinics serving low-income women

Background: More research on sustainment of interventions is needed, especially return on investment (ROI) studies to determine cost-benefit trade-offs for effort required to sustain and how much is gained when effective programs are sustained. The ROSE sustainment (ROSES) study uses a sequential multiple assignment randomized (SMART) design to evaluate the effectiveness and cost-effectiveness of a stepwise approach to sustainment of the ROSE postpartum depression prevention program in 90 outpatient clinics providing prenatal care to pregnant women on public assistance. Postpartum depression (PPD) is common and can have lasting consequences. Outpatient clinics offering prenatal care are an opportune place to provide PPD prevention because most women visit while pregnant. The ROSE (Reach Out, Stay Strong, Essentials for mothers of newborns) program is a group educational intervention to prevent PPD, delivered during pregnancy. ROSE has been found to reduce cases of PPD in community prenatal settings serving low-income pregnant women. Methods: All 90 prenatal clinics will receive enhanced implementation as usual (EIAU; initial training + tools for sustainment). At the first time at which a clinic is determined to be at risk for failure to sustain (i.e., at 3, 6, 9, 12, and 15 months), that clinic will be randomized to receive either (1) no additional implementation support (i.e., EIAU only), or (2) low-intensity coaching and feedback (LICF). If clinics receiving LICF are still at risk at subsequent assessments, they will be randomized to either (1) EIAU + LICF only, or (2) high-intensity coaching and feedback (HICF). Additional follow-up interviews will occur at 18, 24, and 30 months, but no implementation intervention will occur after 18 months. Outcomes include (1) percent sustainment of core program elements at each time point, (2) health impact (PPD rates over time at each clinic) and reach, and (3) ROI (costs and cost-effectiveness) of each sustainment step. Hypothesized mechanisms include sustainment of capacity to deliver core elements and engagement/ownership. Discussion: This study is the first randomized trial evaluating the ROI of a stepped approach to sustainment, a critical unanswered question in implementation science. It will also advance knowledge of implementation mechanisms and clinical care for an at-risk population

Study of Women, Infant feeding, and Type 2 diabetes mellitus after GDM pregnancy (SWIFT), a prospective cohort study: methodology and design

<p>Abstract</p> <p>Background</p> <p>Women with history of gestational diabetes mellitus (GDM) are at higher risk of developing type 2 diabetes within 5 years after delivery. Evidence that lactation duration influences incident type 2 diabetes after GDM pregnancy is based on one retrospective study reporting a null association. The Study of Women, Infant Feeding and Type 2 Diabetes after GDM pregnancy (SWIFT) is a prospective cohort study of postpartum women with recent GDM within the Kaiser Permanente Northern California (KPNC) integrated health care system. The primary goal of SWIFT is to assess whether prolonged, intensive lactation as compared to formula feeding reduces the 2-year incidence of type 2 diabetes mellitus among women with GDM. The study also examines whether lactation intensity and duration have persistent favorable effects on blood glucose, insulin resistance, and adiposity during the 2-year postpartum period. This report describes the design and methods implemented for this study to obtain the clinical, biochemical, anthropometric, and behavioral measurements during the recruitment and follow-up phases.</p> <p>Methods</p> <p>SWIFT is a prospective, observational cohort study enrolling and following over 1, 000 postpartum women diagnosed with GDM during pregnancy within KPNC. The study enrolled women at 6-9 weeks postpartum (baseline) who had been diagnosed by standard GDM criteria, aged 20-45 years, delivered a singleton, term (greater than or equal to 35 weeks gestation) live birth, were not using medications affecting glucose tolerance, and not planning another pregnancy or moving out of the area within the next 2 years. Participants who are free of type 2 diabetes and other serious medical conditions at baseline are screened for type 2 diabetes annually within the first 2 years after delivery. Recruitment began in September 2008 and ends in December 2011. Data are being collected through pregnancy and early postpartum telephone interviews, self-administered monthly mailed questionnaires (3-11 months postpartum), a telephone interview at 6 months, and annual in-person examinations at which a 75 g 2-hour OGTT is conducted, anthropometric measurements are obtained, and self- and interviewer-administered questionnaires are completed.</p> <p>Discussion</p> <p>This is the first, large prospective, community-based study involving a racially and ethnically diverse cohort of women with recent GDM that rigorously assesses lactation intensity and duration and examines their relationship to incident type 2 diabetes while accounting for numerous potential confounders not assessed previously.</p

A haplotype map of allohexaploid wheat reveals distinct patterns of selection on homoeologous genomes

BACKGROUND: Bread wheat is an allopolyploid species with a large, highly repetitive genome. To investigate the impact of selection on variants distributed among homoeologous wheat genomes and to build a foundation for understanding genotype-phenotype relationships, we performed population-scale re-sequencing of a diverse panel of wheat lines. RESULTS: A sample of 62 diverse lines was re-sequenced using the whole exome capture and genotyping-by-sequencing approaches. We describe the allele frequency, functional significance, and chromosomal distribution of 1.57 million single nucleotide polymorphisms and 161,719 small indels. Our results suggest that duplicated homoeologous genes are under purifying selection. We find contrasting patterns of variation and inter-variant associations among wheat genomes; this, in addition to demographic factors, could be explained by differences in the effect of directional selection on duplicated homoeologs. Only a small fraction of the homoeologous regions harboring selected variants overlapped among the wheat genomes in any given wheat line. These selected regions are enriched for loci associated with agronomic traits detected in genome-wide association studies. CONCLUSIONS: Evidence suggests that directional selection in allopolyploids rarely acted on multiple parallel advantageous mutations across homoeologous regions, likely indicating that a fitness benefit could be obtained by a mutation at any one of the homoeologs. Additional advantageous variants in other homoelogs probably either contributed little benefit, or were unavailable in populations subjected to directional selection. We hypothesize that allopolyploidy may have increased the likelihood of beneficial allele recovery by broadening the set of possible selection targets

Three new pyridoacridine type alkaloids from a Singaporean ascidian

Two new pyridoacridine alkaloids, kuanomamines E and F, and a new ring opened pyridoacridine alkaloid, subarine, were isolated from a Singaporean ascidian Also isolated were known pyridoacridine alkaloids ascididemin and kuanomammes A and D The structures of the alkaloids were determined by spectroscopic methods

Encapsulation of Aromatic Compounds and a Non-Aromatic Herbicide into a Gadolinium-Based Metal–Organic Framework via the Crystalline Sponge Method

The crystalline sponge method (CSM) is a procedure that has the potential to remove the need to have good-quality single crystals of the target compound by soaking said compound into a crystalline metal–organic framework (MOF). To increase the range of compounds that can be employed with the CSM, a range of different MOFs must be investigated. In this study we have explored the use of a lanthanide-based MOF, RUM-2, recently shown to have potential as a CSM host. Specifically, we have successfully formed five novel inclusion complexes with the four aromatic guests: 2-phenylethanol, benzyl acetate, benzyl benzoate, and vanillin and the non-aromatic herbicide molinate. A detailed analysis of the effect of size on the positions guest molecules sit within the pores of the MOF was performed. The π···π, CH···π, hydrogen-bonding, and coordination host–guest and guest–guest interactions utilized in guest ordering were also investigated, and the disorder experienced by guest molecules was documented

Forty years of problem-oriented policing: A review of progress in England and Wales

This article analyses and critically reflects on the position of problem-oriented policing within England and Wales. Problem-oriented policing is a framework for improving police effectiveness. Its adoption has consistently been shown to be associated with sizable reductions in a wide range of crimes and public safety issues. However, many studies also find that problem-oriented policing is difficult to embed and sustain within police organisations. This article draws on the experiences and perspectives of 86 informed stakeholders to critically examine the position and practice of problem-oriented policing 40 years after its original formulation by Herman Goldstein in 1979. We argue that despite evidence of renewed interest in problem-oriented policing, the approach is not habitually conducted within police organisations in England and Wales. Where it is conducted, the practice of problem-oriented policing is found to lack discipline, the processes tend not to be faithfully followed, and there are weaknesses at all stages of the process. Implications of the findings for future research and police practice are discussed