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The emergence of new psychoactive substances into the global drug market has presented challenges for effective drug legislation and enforcement. One approach to prohibition uses controlled drug analogue legislation, which involves assessing the structural similarity of new substances compared to listed controlled drugs, as opposed to the new substance being specifically listed in legislation itself. An issue arises of there being no clear definition for what constitutes similarity between two substances, and as such, there is level of subjectivity in any decision made. This paper outlines the global and local drug scene in New Zealand, including the emergence of new psychoactive substances, and the legislation that is available for the control of illicit substances in a New Zealand context and the current method for considering new psychoactive substances as potential controlled drug analogues. The authors go on to propose an alternative method to this assessment process, which involves an objective and reproducible similarity scoring mechanism. [ABSTRACT FROM AUTHOR]

BackgroundRetinoids enhance differentiation of most epithelial tissues. Epidemiologic studies have shown an inverse relationship between dietary intake or serum levels of vitamin A and the development of cervical dysplasia and/or cervical cancer. Pilot and phase I investigations demonstrated the feasibility of the local delivery of all-trans-retinoic acid (RA) to the cervix using a collagen sponge insert and cervical cap. A phase II trial produced a clinical complete response rate of 50%.PurposeThis randomized phase III trial was designed to determine whether topically applied RA reversed moderate cervical intraepithelial neoplasia (CIN) II or severe CIN.MethodsAnalyses were based on 301 women with CIN (moderate dysplasia, 151 women; severe dysplasia, 150 women), evaluated by serial colposcopy, Papanicolaou cytology, and cervical biopsy. Cervical caps with sponges containing either 1.0 mL of 0.372% beta-trans-RA or a placebo were inserted daily for 4 days when women entered the trial, and for 2 days at months 3 and 6. Patients receiving treatment and those receiving placebo were similar with respect to age, ethnicity, birth-control methods, histologic features of the endocervical biopsy specimen and koilocytotic atypia, and percentage of involvement of the cervix at study. Treatment effects were compared using Fisher's exact test and logistic regression methods. Side effects were recorded, and differences were compared using Fisher's exact test.ResultsRA increased the complete histologic regression rate of CIN II from 27% in the placebo group to 43% in the retinoic acid treatment group (P = .041). No treatment difference between the two arms was evident in the severe dysplasia group. More vaginal and vulvar side effects were seen in the patients receiving RA, but these effects were mild and reversible.ConclusionsA short course of locally applied RA can reverse CIN II, but not more advanced dysplasia, with acceptable local side effects.ImplicationsA derivative of vitamin A can reverse or suppress an epithelial preneoplasia, lending further support to the notion that chemoprevention of human cancer is feasible.

Background: The active metabolite of vitamin D 1α,25-dihydroxycholecalciferol (1,25D(3) ) has exhibited broad-spectrum antitumor activity in xenograft animal models. However, its activity against metastatic disease has not been extensively investigated.Methods: Squamous cell carcinoma (SCC) or 1,25D(3) -resistant variant SCC-DR cells were treated with 1,25D(3) . Actin organization was examined by immunofluorescence assay. Cell migration was assessed by "wound" healing and chemotactic migration assays. Cell invasion was assessed by a Matrigel-based invasion assay and in situ zymography. Matrix metalloproteinase 2 (MMP-2) and MMP-9 expression and secretion were examined by immunoblot analysis and an enzyme-linked immunosorbent assay, respectively. E-cadherin expression was assessed by flow cytometry, immunoblot analysis, and immunohistochemistry. Knockdown of E-cadherin was achieved by small interfering RNA. An experimental metastasis mouse model was created by intravenous injection of tumor cells; and lung tumor development in the mice was assessed by magnetic resonance imaging, gross observation, and histology.Results: SCC cellular morphology and actin organization were altered by 10 nM 1,25D(3) . 1,25D(3) inhibited SCC cell motility and invasion, which were associated with reduced expression and secretion of MMP-2 and MMP-9, and 1,25D(3) promoted the expression of E-cadherin. These findings were not observed in SCC-DR cells. Knock down of E-cadherin rescued 1,25D(3) -inhibited cell migration. Intravenous injection of SCC or SCC-DR cells resulted in the establishment of extensive pulmonary lesions in saline-treated C3H mice. Treatment with 1,25D(3) resulted in a marked reduction in the formation of lung tumor colonies in mice that were injected with SCC cells, but not in mice that were injected with SCC-DR cells.Conclusions: 1,25D(3) suppressed SCC cell motility, invasion, and metastasis, partially through the promotion of E-cadherin-mediated cell-cell adhesion. [ABSTRACT FROM AUTHOR]

Background: 1,25 dihydroxyvitamin D3 (1,25D3) potentiates the cytotoxic effects of several common chemotherapeutic agents. The combination of gemcitabine and cisplatin is a current standard chemotherapy regimen for bladder cancer. The authors investigated whether 1,25D3 could enhance the antitumor activity of gemcitabine and cisplatin in bladder cancer model systems.Methods: Human bladder cancer T24 and UMUC3 cells were pretreated with 1,25D3 followed by gemcitabine and cisplatin. Apoptosis was assessed by annexin V staining. Caspase activation was examined by immunoblot analysis and substrate-based caspase activity assay. The cytotoxic effects were examined by using 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and in vitro clonogenic assay. p73 protein levels were assessed by immunoblot analysis. Knockdown of p73 was achieved by siRNA. The in vivo antitumor activity was assessed by in vivo excision clonogenic assay and tumor regrowth delay in the T24 xenograft model.Results: 1,25D3 pretreatment enhanced gemcitabine and cisplatin-induced apoptosis and the activities of caspases 8, 9, and 3 in T24 and UMUC3 cells. 1,25D3 synergistically reduced gemcitabine and cisplatin-suppressed surviving fraction in T24 cells. 1,25D3, gemcitabine, or cisplatin induced p73 accumulation, which was enhanced by gemcitabine and cisplatin or 1,25D3 and gemcitabine and cisplatin. p73 expression was lower in human primary bladder tumor tissue compared with adjacent normal tissue. Knockdown of p73 increased clonogenic capacity of T24 cells treated with 1,25D3, gemcitabine and cisplatin, or 1,25D3 and gemcitabine and cisplatin. 1,25D3 and gemcitabine and cisplatin combination enhanced tumor regression compared with 1,25D3 or gemcitabine and cisplatin alone.Conclusions: 1,25D3 potentiates gemcitabine and cisplatin-mediated growth inhibition in human bladder cancer models in vitro and in vivo, which involves p73 induction and apoptosis. [ABSTRACT FROM AUTHOR]

Considerable preclinical and epidemiologic data suggest that vitamin D may play a role in the pathogenesis, progression, and therapy for cancer. Numerous epidemiologic studies support the hypothesis that individuals with lower serum vitamin D levels have a higher risk of a number of cancers. Measures of vitamin D level in such studies include both surrogate estimates of vitamin D level (residence in more northern latitudes, history of activity, and sun exposure) as well as measured serum 25(OH) cholecalciferol levels. Perhaps, the most robust of these epidemiologic studies is that of Giovannucci et al, who developed and validated an estimate of serum 25(OH) cholecalciferol level and reported that among >40,000 individuals in the Health Professionals Study, an increase in 25(OH) cholecalciferol level of 62.5 ng/mL was associated with a reduction in the risk of head/neck, esophagus, pancreas cancers, and acute leukemia by >50%. Unfortunately, very limited data are available to indicate whether or not giving vitamin D supplements reduces the risk of cancer. Many preclinical studies indicate that exposing cancer cells, as well as vascular endothelial cells derived from tumors, to high concentrations of active metabolites of vitamin D halts progression through cell cycle, induces apoptosis and will slow or stop the growth of tumors in vivo. There are no data that one type of cancer is more or less susceptible to the effects of vitamin D. Vitamin D also potentiates the antitumor activity of a number of types of cytotoxic anticancer agents in in vivo preclinical models. Vitamin D analogues initiate signaling through a number of important pathways, but the pathway(s) essential to the antitumor activities of vitamin D are unclear. Clinical studies of vitamin D as an antitumor agent have been hampered by the lack of a suitable pharmaceutical preparation for clinical study. All commercially available formulations are inadequate because of the necessity to administer large numbers of caplets and the poor "bioavailability" of calcitriol (the most carefully studied analogue) at these high doses. Preclinical data suggest that high exposures to calcitriol are necessary for the antitumor effects. Clinical data do indicate that high doses of calcitriol (>100 mcg weekly, intravenously, and 0.15 microg /kg weekly, orally) can be given safely. The maximum tolerated dose of calcitriol is unclear. While a 250-patient trial in men with castration-resistant prostate cancer comparing docetaxel (36 mg/sqm weekly) +/- calcitriol 0.15 microg/kg indicated that calcitriol was very safe may have reduced to death rate, an adequately powered (1000 patients) randomized study of weekly docetaxel + calcitriol versus q3 week docetaxel was negative. The limitations of this trial were the unequal chemotherapy arms compared in this study and the failure to use an optimal biologic dose or maximum-tolerated dose of calcitriol. In view of the substantial preclinical and epidemiologic data supporting the potential role of vitamin D in cancer, careful studies to evaluate the impact of vitamin D replacement on the frequency of cancer and the impact of an appropriate dose and schedule of calcitriol or other active vitamin D analogue on the treatment of established cancer are indicated. [ABSTRACT FROM AUTHOR]

This study examined the efficacy of a condensed version of the Seeking Safety intervention in the reduction of trauma-related symptoms and improved drug abstinence rates among women in residential chemical dependence treatment. One hundred and four women were randomly assigned to treatment including a condensed (six session) Seeking Safety intervention or the standard chemical dependence intervention. The Seeking Safety participants reported lower sexual-abuse-related trauma symptoms at 30 days posttreatment as compared to participants who received only standard treatment. However, the condensed Seeking Safety intervention was not more advantageous in reducing overall trauma symptoms or relapse 30 days after treatment ended. [ABSTRACT FROM AUTHOR]

Several osteoporosis risk-factor screening tools have been developed to identify women at increased risk of low bone mineral density, who would most benefit from dual x-ray absorptiometry (DXA) screening. The purpose of this systematic review was to assess the effectiveness of these screening tools in determining postmenopausal Caucasian women at risk of developing osteoporosis. Appropriate databases and sources of primary studies were identified. A systematic review of the literature using a comprehensive search strategy was employed, and all citations were stored. Exclusion criteria were established, and critical quality was assessed. Study characteristics were tabulated and comparisons made. Upon reviewing the evidence, 6 screening tools (Simple Calculated Osteoporosis Risk Estimation, the Osteoporosis Risk Assessment Instrument, the Osteoporosis Self-Assessment Tool [OST], the body weight criterion, the Osteoporosis Index of Risk, and Age, Body Size, No Estrogen) were identified. Studies show that these screening tools are useful in identifying postmenopausal Caucasian women in need of DXA screening and possible intervention for osteoporosis. For clinical and community practice, the OST is the simplest approach to determine individuals at risk of osteoporosis and in need of DXA screening. There is still a need for further development and validation of screening tools in both men and ethnicities other than Caucasian. [ABSTRACT FROM AUTHOR]

The Centre for Epidemiological Studies Depression Scale (CES-D) is a widely used self-report scale to assess depressive symptom levels among the general population. The purposes of the study are to explore the factor structure of CES-D in a population-based Canadian sample and to compare focal constructs of CES-D across age and gender. Confirmatory factor analysis supported the four-factor structure of the CES-D across three age categories and both genders. Subscales scores, however, showed important differences primarily based on gender. Attending to these specific symptom dimensions could help explain known gender differences in depression. [ABSTRACT FROM AUTHOR]

PURPOSE: The aim of this study is to present an analysis investigating the association of patient characteristics with overall survival (OS) in individuals with stage III non–small-cell lung cancer (NSCLC). PATIENTS AND METHODS: Ten prognostic factors were analyzed in 203 patients with NSCLC who were enrolled in a phase III trial conducted by the Hoosier Oncology Group and US Oncology between 2002 and 2006. Eligible patients had untreated stage III NSCLC, forced expiratory volume in one second (FEV1) &nvge; 1 liter, baseline performance status of 0/1, and weight loss < 5% in 3 months preceding the trial. Univariate analysis, Cox proportional hazards regression, and parametric accelerated failure time models were performed to identify the factors that affected survival duration. Variables analyzed included age (< 70 years vs. &nvge; 70 years), sex, ethnicity, body mass index, performance status (0 vs. 1), FEV1 (> 2 L vs. 1-2 L), smoking status (current vs. never/former), hemoglobin (Hb) level, use of positron emission tomography scan in staging, and stage (IIIA vs. IIIB). RESULTS: Median follow-up was 25.6 months and the median OS was 21.2 months. The univariate analysis showed that Hb levels &nvge; 12 were associated with an improved survival (P = .033). The multivariable parametric accelerated failure time model demonstrated the association of FEV1 > 2 L (P = .014), and higher pretreatment Hb values (P = .007) as independent prognostic factors for OS. Similarly in the Cox regression, survival was influenced by Hb and FEV1 > 2 L. CONCLUSION: This analysis suggests that FEV1 > 2 L and higher pretreatment Hb values are associated with improved OS in patients with stage III NSCLC. These factors can be useful in predicting for more favorable outcomes in patients with stage III NSCLC and provide additional information when designing future studies. [ABSTRACT FROM AUTHOR]

The purpose of this study was to assess the profile of home support workers (HSWs) caring for the frail elderly and to determine the perceived empowerment levels and general health knowledge of these support workers. Background, work-profile, empowerment level and health knowledge related to seniors of 64 HSWs were assessed using questionnaires. Findings revealed the majority of workers to be middleaged women, and their health knowledge scores were low. Empowerment levels were moderate as was formal power. Findings demonstrate the need to revise the curriculum of HSWs to include health topics, as well as the need for continued education and strategies to enhance empowerment levels. [ABSTRACT FROM AUTHOR]

Few studies have examined older women's body image. This study compared body image dissatisfaction (BID) and weight control practices; evaluated associations among BID, societal influences and concern for appropriateness (CFA); and identified the most important correlate of BID among younger (19-23) and older women (65-74). Questionnaires obtained information on demographics, weight control practices, societal influences (SATAQ-3), CFA and BID using the Figure Rating Scale. Findings revealed no difference in the prevalence of BID. The number of weight control practices and SATAQ-3 and CFA scores were correlated to BID. Pressure from the media was the most significant correlate of BID. [ABSTRACT FROM AUTHOR]

OBJECTIVES: Our study tested the effectiveness of network methods for identifying opinion leaders and for constructing groups. METHODS: Three conditions-random, teacher, and network--ere randomly assigned to 84 6th-grade classrooms within 16 schools. Pre- and postcurriculum data on mediators of tobacco use were collected from 1961 students. Peer leaders in the network condition were identified by student nominations, and those leaders were matched with the students who nominated them. RESULTS: Students in the network condition relative to the random condition liked the prevention program more and had improved attitudes (beta = -0.06; P <.01), improved self-efficacy (beta = -0.10; P <.001), and decreased intention to smoke (adjusted odds ratio [OR] = 0.46; 95% confidence interval [CI] = 0.38, 0.55). CONCLUSIONS: The network method was the most effective way to structure the program. Future programs may refine this technique and use it in other settings. [ABSTRACT FROM AUTHOR]

The feasibility of using an electronic device to self-monitor diet and fluid intake was assessed using the treatment implementation model. The three patients on hemodialysis who participated in this pilot study were asked to self-monitor diet and fluid intake for 12 weeks with a personal digital assistant. The intervention was delivered as intended; however, participants reported problems with usability, and compliance to self-monitoring was lower than desirable. Further adjustments to the intervention will be made before testing efficacy. [ABSTRACT FROM AUTHOR]

This retrospective study describes patterns of interdialytic weight gain (IWG) over the first year of hemodialysis in 27 individuals. IWG increased over the first 12 weeks and appeared to reverse after 12 weeks, increasing again after 32 weeks. Interventions may need to occur after the individual has been receiving treatment for 12 weeks; booster interventions may be indicated after 32 weeks. Variability in the two measures used (mean daily interdialytic weight gain and mean daily percent above dry weight) suggests a need for further study. [ABSTRACT FROM AUTHOR]

Adult haematopoietic stem cells (HSCs) are responsible for the lifelong production of blood and immune cells, a process regulated by extracellular cues including cytokines. Many cytokines signal through the conserved JAK/STAT pathway, in which tyrosine-phosphorylated STATs (pSTATs) function as transcription factors. STAT5 is a pivotal downstream mediator of several cytokines known to regulate haematopoiesis but its function in the HSC compartment remains poorly understood. Here, we show that STAT5-deficient HSCs exhibit an unusual phenotype: reduced multi-lineage repopulation and self-renewal, combined with reduced exit from quiescence and increased differentiation. This was driven not only by loss of canonical pSTAT5 signalling, but also by loss of distinct transcriptional functions mediated by STAT5 lacking canonical tyrosine phosphorylation (uSTAT5). Consistent with this concept, expression of an unphosphorylatable STAT5 mutant constrained wild-type HSC differentiation, promoted their maintenance and upregulated transcriptional programs associated with quiescence and stemness. The JAK1/2 inhibitor, ruxolitinib, which increased the uSTAT5:pSTAT5 ratio, had similar effects on murine HSC function: it constrained HSC differentiation and proliferation, promoted HSC maintenance and upregulated transcriptional programs associated with stemness. Ruxolitinib also enhanced serial replating of normal human HSPCs, CALR-mutant murine HSCs and HSPCs obtained from patients with myelofibrosis. Our results therefore reveal a previously unrecognized interplay between pSTAT5 and uSTAT5 in the control of HSC function and highlight JAK inhibition as a potential strategy for enhancing HSC function during ex vivo culture. Increased levels of uSTAT5 may also contribute to the failure of JAK inhibitors to eradicate myeloproliferative neoplasms., (Copyright © 2024 American Society of Hematology.)

Abstract: Loss of long-term hematopoietic stem cell (LT-HSC) function ex vivo hampers the success of clinical protocols that rely on culture. However, the kinetics and mechanisms through which this occurs remain incompletely characterized. In this study, through time-resolved single-cell RNA sequencing, matched in vivo functional analysis, and the use of a reversible in vitro system of early G1 arrest, we defined the sequence of transcriptional and functional events that occur during the first ex vivo division of human LT-HSCs. We demonstrated that the sharpest loss in LT-HSC repopulation capacity happens early on, between 6 and 24 hours of culture, before LT-HSCs commit to cell cycle progression. During this time window, LT-HSCs adapt to the culture environment, limit the global variability in gene expression, and transiently upregulate gene networks involved in signaling and stress responses. From 24 hours, LT-HSC progression past early G1 contributes to the establishment of differentiation programs in culture. However, contrary to the current assumptions, we demonstrated that the loss of HSC function ex vivo is independent of cell cycle progression. Finally, we showed that targeting LT-HSC adaptation to culture by inhibiting the early activation of JAK/STAT signaling improves HSC long-term repopulating function ex vivo. Collectively, our study demonstrated that controlling early LT-HSC adaptation to ex vivo culture, for example, via JAK inhibition, is critically important to improve HSC gene therapy and expansion protocols., (© 2024 American Society of Hematology. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).)

Three-dimensional (3D) modeling is a recent, innovative approach to teaching anatomy. There is little literature, however, to suggest how 3D modeling is best used to teach students and whether or not students can gain the same level of understanding as they might use more traditional, hands-on, teaching methods. This study evaluated the use of a 3D modeling software in both a flipped classroom curriculum and as an active learning tool in comparison to traditional, physical model-based teaching. Pre- and post-course content-based assessments were used to evaluate students' learning. Our findings indicated no significant difference between standard and flipped classroom learning; however, the students who used 3D modeling software as an active learning tool significantly underperformed students in the standard group (F(2,1060) = 112.43, p < 0.0001). These findings suggest that these technologies may not yet be useful as a primary means of instruction. Possible explanations may include cognitive overload in navigating the system, intrinsic limitations of the software, or other factors. Further development and research of these technologies is necessary prior to their adoption into teaching practices in anatomy., (© 2024 American Association for Anatomy.)

Background: Hallux valgus is a common condition with a complex etiology resulting in numerous treatment options. Recurrence of the deformity can occur following correction. Surgical technique and possibly also postoperative care play a role in reducing recurrence rates. This article highlights a postoperative surgical dressing technique which allows for semirigid support during the immediate postoperative period., Methods: A wooden tongue depressor placed along the medial border of the hallux comprises the primary support for the dressing. The rigidity of the tongue depressor allows for the hallux to be drawn toward the depressor, encouraging neutral alignment of the hallux. Dressings are removed 2 weeks postoperatively, with new dressings applied in similar fashion and maintained in place until 6 weeks postoperatively., Results: Based upon our observations, our surgical dressing technique provides sufficient support following hallux valgus correction surgery while being straightforward to replicate without the need for frequent dressing changes. The dressing materials are of negligible cost and are typically readily available. No associated wound complications have been observed., Conclusions: We present an easily replicable and affordable option for postoperative hallux valgus correction surgical dressings., Levels of Evidence: Level V: Expert Opinion., Competing Interests: Declaration of Conflicting InterestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

In 2003, the Human Disease Ontology (DO, https://disease-ontology.org/) was established at Northwestern University. In the intervening 20 years, the DO has expanded to become a highly-utilized disease knowledge resource. Serving as the nomenclature and classification standard for human diseases, the DO provides a stable, etiology-based structure integrating mechanistic drivers of human disease. Over the past two decades the DO has grown from a collection of clinical vocabularies, into an expertly curated semantic resource of over 11300 common and rare diseases linking disease concepts through more than 37000 vocabulary cross mappings (v2023-08-08). Here, we introduce the recently launched DO Knowledgebase (DO-KB), which expands the DO's representation of the diseaseome and enhances the findability, accessibility, interoperability and reusability (FAIR) of disease data through a new SPARQL service and new Faceted Search Interface. The DO-KB is an integrated data system, built upon the DO's semantic disease knowledge backbone, with resources that expose and connect the DO's semantic knowledge with disease-related data across Open Linked Data resources. This update includes descriptions of efforts to assess the DO's global impact and improvements to data quality and content, with emphasis on changes in the last two years., (© The Author(s) 2023. Published by Oxford University Press on behalf of Nucleic Acids Research.)

Background: The nucleus accumbens (NAc) is an important region in motivation and reward. Glutamatergic inputs from the infralimbic cortex (ILC) to the shell region of the NAc (NAcSh) have been implicated in driving the motivation to seek reward through repeated action-based behavior. While this has primarily been studied in males, observed sex differences in motivational circuitry and behavior suggest that females may be more sensitive to rewarding stimuli. These differences have been implicated for the observed vulnerability in women to substance use disorders., Methods: We used an optogenetic self-stimulation task in addition to ex vivo electrophysiological recordings of NAcSh neurons in mouse brain slices to investigate potential sex differences in ILC-NAcSh circuitry in reward-seeking behavior. Glutamatergic neurons in the ILC were infected with an AAV delivering DNA encoding for channelrhodopsin. Entering the designated active corner of an open field arena resulted in photostimulation of the ILC terminals in the NAcSh. Self-stimulation occurred during two consecutive days of testing over three consecutive weeks: first for 10 Hz, then 20 Hz, then 30 Hz. Whole-cell recordings of medium spiny neurons in the NAcSh assessed both optogenetically evoked local field potentials and intrinsic excitability., Results: Although both sexes learned to seek the active zone, within the first day, females entered the zone more than males, resulting in a greater amount of photostimulation. Increasing the frequency of optogenetic stimulation amplified female reward-seeking behavior. Males were less sensitive to ILC stimulation, with higher frequencies and repeated days required to increase male reward-seeking behavior. Unexpectedly, ex vivo optogenetic local field potentials in the NAcSh were greater in slices from male animals. In contrast, female medium-spiny neurons (MSNs) displayed significantly greater intrinsic neuronal excitability., Conclusions: Taken together, these data indicate that there are sex differences in the motivated behavior driven by glutamate within the ILC-NAcSh circuit. Though glutamatergic signaling was greater in males, heightened intrinsic excitability in females appears to drive this sex difference., (© 2023. The Author(s).)

The development of new methods of catalyst synthesis with the potential to generate active site structures orthogonal to those accessible by traditional protocols is of great importance for discovering new materials for addressing challenges in the evolving energy and chemical economy. In this work, the generality of oxidative grafting of organometallic and well-defined molecular metal precursors onto redox-active surfaces such as manganese dioxide (MnO 2 ) and lithium manganese oxide (LiMn 2 O 4 ) is investigated. Nine molecular metal precursors are explored, spanning groups 4-11 and each of the three periods of the transition metal series. The byproducts of the oxidative grafting reaction, a mixture of protodemetalation and ligand homocoupling for several organometallic precursors, was found to provide insights into the mechanism of the grafting reaction, suggesting oxidation of both the metal d-orbitals, as well as the metal-carbon σ-bonds, resulting in ejection of the ligand radical fragment. Analysis of the supported structures and oxidation state by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) suggests that several of the chemisorbed metal ions are intercalated into interstitial vacancies of the surface structure while other complexes form intact molecular fragments on the surface. Proof of concept for the use of this metalation protocol to generate diverse, metal-dependent catalytic performance is demonstrated by the application of these materials in the conversion of cyclohexane to K/A oil (cyclohexanol and cyclohexanone) with tert -butyl hydroperoxide, as well as in the low-temperature ( T ≤ 50 °C) oxidation of carbon monoxide to carbon dioxide.

Most commercial flue-cured tobacco cultivars contain the Rk1 resistance gene, which provides resistance to races 1 and 3 of Meloidogyne incognita and race 1 of M. arenaria . A number of cultivars now possess a second root-knot resistance gene, Rk2 . High soil temperatures have been associated with a breakdown of root-knot resistance genes in a number of crops. Three greenhouse trials were performed from 2014 to 2015 investigate the effect of high soil temperature on the efficacy of Rk1 and/or Rk2 genes in reducing parasitism by a population of M. incognita race 3. Trials were arranged in randomized complete block design in open-top growth chambers set at 25°, 30°, and 35°C. Plants were inoculated with 3,000 eggs and data were collected 35 days post-inoculation. Galling, numbers of egg masses and eggs, and reproductive index were compared across cultivar entries. Nematode reproduction was reduced at 25°C and 30°C on entries possessing Rk1 and Rk1Rk2 compared to the susceptible entry and the entry possessing only Rk2 . However, there were often no significant differences in reproduction at 35°C between entries with Rk1 and/or Rk2 compared to the susceptible control, indicating an increase of root-knot nematode parasitism on resistant entries at higher temperatures. Although seasonal differences in nematode reproduction were observed among experiments, relative differences among tobacco genotypes remained generally consistent., (© 2023 Jill R. Pollok et al., published by Sciendo.)