A study of the reaction of [Ni(NHC)] synthons with the heterocumulene CS is reported. Nickel complexes of η-(C-S) coordinated CS, [Ni(NHC)(η-CS)] (NHC = IiPr (1a), IiPr (1b)) were obtained from the reaction of CS with precursors of [Ni(NHC)] (NHC = IiPr, IiPr). The result of this reaction critically depends on the NHC employed, as [Ni(IMes)], the complex of the sterically more demanding -aryl substituted NHC IMes, led to formation of the dinuclear complex [{Ni(IMes)(μ-CS)}] (2d).
View Article and Find Full Text PDFHuman papillomavirus (HPV)-negative head and neck squamous cell carcinoma (HNSCC) is the sixth most common cancer type in the world and is associated with an overall poor prognosis. The protein methyltransferase SET and MYND domain-containing 3 (SMYD3), which trimethylates H3K4, activates gene transcription and enhances several oncogenic pathways, including epithelial-mesenchymal transition and cell cycle related pathways, in various cancer types. It was also recently shown that SMYD3 is overexpressed in HPV-negative HNSCC, and represses the expression of type I IFN response genes, contributing to resistance to anti-PD-1 checkpoint blockade in this disease.
View Article and Find Full Text PDFThe 1,1-azoliumdithiocarboxylate cAAC-CS (1a) was prepared and its redox chemistry was evaluated and compared to NHC based dithiocarboxylates IDipp-CS (1b) and IMes-CS (1c). Radical anions [carbene-CS]˙ were prepared by metallic reduction as the potassium or magnesium ion complexes [K(18-crown-6)(cAAC-CS)] (2a), [K(18-crown-6)(NHC-CS)] (NHC = IDipp: 2b, IMes: 2c), and [Mg(NacNac)(cAAC-CS)] (3) and extensively characterized (SC-XRD, EPR, UV/VIS/NIR, DFT). These complexes represent the first examples of isolated radical anions of 1,1-dithiolenes.
View Article and Find Full Text PDFSET and MYND-domain containing protein 3 (SMYD3) mediates epigenetic repression of type I IFN response genes in human papillomavirus (HPV)-negative HNSCC cells, and Smyd3 depletion using anti-sense oligonucleotides (ASOs) increases the sensitivity of syngeneic mouse oral carcinoma (MOC1) models to anti-PD-1 therapy. In this study, we utilized single-cell RNA-seq of MOC1 tumors treated with Smyd3 ASOs and found enrichment of type I IFN response pathways in cancer cells, a shift of CD8 T-cells toward an activated/memory phenotype, and a shift of neutrophils toward an anti-tumorigenic phenotype. Mechanisms of resistance to the Smyd3 ASO and anti-PD-1 combination were derived from cancer cells, macrophages, and CD8 T-cells, including neutrophil enrichment through the upregulation of , repression of and defective antigen presentation.
View Article and Find Full Text PDFThe tetracyanoborate anion [B(CN)] (TCB) was utilized as a building block for the synthesis of polynuclear chromium carbonyl compounds upon photolytic reaction with [Cr(CO)]. Up to four κN-coordinated cyano groups of TCB can be involved in binding to chromium, giving mixtures of [B(CN){CN-Cr(CO)}] ( = 1-4; 1-4) and [{Cr(CO)(B(CN))}] (5). The reaction of [B(CN)] with -[Cr(CO)(MeCN)] led to isolation of salts of the tetraanionic heterocubane cage [{Cr(CO)(B(CN))}].
View Article and Find Full Text PDFBackground: Robust collateral circulation has been linked with better reperfusion and clinical outcomes. It remains unclear how individual assessments of collateral circulation may be translated into clinical practice.
Methods: The pooled Highly Effective Reperfusion Evaluated in Multiple Endovascular Stroke Trials (HERMES) angiography dataset was analyzed by a centralized, independent imaging core blinded to other clinical data.
Background: Few clinical studies perform detailed analyses of subtypes of intracranial hemorrhage (ICH) after mechanical thrombectomy (MT) used to treat acute ischemic stroke. Symptomatic intracranial hemorrhage (sICH) is a formidable complication of MT and is widely used in clinical trials as a safety outcome. However, variable definitions of sICH are used across clinical studies.
View Article and Find Full Text PDFA comprehensive study on the synthesis and characterization of NHC-ligated nickel(II) cyanoborates (CBs) is presented (NHC = N-heterocyclic carbene). Nickel(II) cyanoborates Ni[BH(CN)]·HO (Ib·HO), Ni[BH(CN)]·0.5HO (Ic·0.
View Article and Find Full Text PDFNickel(II) cyanoborates Ni[BH(CN)]·HO (·HO), Ni[BH(CN)]·0.5HO (·0.5HO), and Ni[B(CN)]·0.
View Article and Find Full Text PDFThe synthesis and characterization of a series of Cr(II) N-Heterocyclic Carbene (NHC) complexes of the type [{Cr(NHC)Cl(μ-Cl)}] and [(Cyp)Cr(NHC)X] (Cyp = η-CH, cyclopentadienyl; η-CMe, pentamethylcyclopentadienyl; X = Cl, η-CH; NHC = IMe, IiPr, IMes, IDipp) as well as the cyclic (alkyl)(amino)carbene cAAC ligated complexes [(η-CH)Cr(cAAC)X] (X = Cl, NPh), [(η-CH)Cr(cAAC)Cl] (CH = Ind, indenyl) and [(η-CH)Cr(cAAC)Cl] (CH = Fl, fluorenyl) are reported. The reduction of [(η-CMe)Cr(IMe)Cl] with KC in the presence of CO afforded the NHC ligated Cr(I) metallo-radical [(η-CMe)Cr(IMe)(CO)]. Quantum chemical calculations performed on [(η-CMe)Cr(IMe)(CO)] confirm for this complex a predominantly chromium centered radical.
View Article and Find Full Text PDFLaryngoscope Investig Otolaryngol
August 2023
Objective: This study aimed to assess if oil (NSO), a health supplement containing thymoquinone as a major component, can act as a protective agent in salivary gland stem cells following radiotherapy (RT) damage.
Methods: Forty, 10-week-old, male C3H/HeJ mice were randomized to four experimental groups: sham RT + HO gavage (control) ( = 4); 15 Gy RT + HO gavage ( = 12); sham RT + NSO gavage ( = 12); and 15 Gy RT + NSO gavage ( = 12). Weight changes, saliva production, and salivary gland histopathologic staining were recorded for each group over the course of the experiment.
Background: Nocturnal enuresis (NE) is a frequent diagnosis in pediatric and adolescent populations with an estimated prevalence of around 15% at the age of 6 years. NE can have a substantial impact on multiple health domains. Bedwetting alarms, which typically consist of a sensor and moisture-activated alarm, are a common treatment.
View Article and Find Full Text PDFBackground: Recent studies examining treatment disparities in thyroid cancer care found that appropriate use of surgery and radioactive iodine may be improving over time.
Methods: California Cancer Registry and California Office of Statewide Health Planning and Development data was evaluated for the effect of race on overall and disease-specific survival for thyroid cancer in California (1999-2017). Reoperation data was also examined.
Head and neck cancer is the sixth most common cancer in the world, with more than 300,000 deaths attributed to the disease annually. Aggressive surgical resection often with adjuvant chemoradiation is the cornerstone of treatment. However, the necessary chemoradiation treatment can result in collateral damage to adjacent vital structures causing a profound impact on quality of life.
View Article and Find Full Text PDFBackground: The rise of direct-to-consumer genetic testing has enabled many to learn of their possible increased risk for rare diseases, some of which may be suitable for gene-targeted therapies. However, recruiting a large and representative population for rare diseases or genetically defined sub-populations of common diseases is slow, difficult, and expensive.
Objective: To assess the feasibility of recruiting and retaining a cohort of individuals who carry a genetic mutation linked to Parkinson's disease (G2019S variant of LRRK2); to characterize this cohort relative to the characteristics of traditional, in-person studies; and to evaluate this model's ability to create an engaged study cohort interested in future clinical trials of gene-directed therapies.
The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides.
View Article and Find Full Text PDFCarabids and other epigeal arthropods make important contributions to biodiversity, food webs and biocontrol of invertebrate pests and weeds. Pitfall trapping is widely used for sampling carabid populations, but this technique yields biased estimates of abundance ('activity-density') because individual activity - which is affected by climatic factors - affects the rate of catch. To date, the impact of temperature on pitfall catches, while suspected to be large, has not been quantified, and no method is available to account for it.
View Article and Find Full Text PDFFlagellate green algae have developed a visual system, the eyespot apparatus, which allows the cell to phototax. To further understand the molecular organization of the eyespot apparatus and the phototactic movement that is controlled by light and the circadian clock, a detailed understanding of all components of the eyespot apparatus is needed. We developed a procedure to purify the eyespot apparatus from the green model alga Chlamydomonas reinhardtii.
View Article and Find Full Text PDFPredictions of plant and animal species distributions are important for conservation and for the assessment of large-scale ecosystem change. Land cover data are becoming more widely available for use in land management and conservation. We use a logistic regression modelling approach to investigate the utility of these data for modelling.
View Article and Find Full Text PDFBody weight and traits associated with production of wool were measured over a 2-year period between 1985 and 1987 in south-western New South Wales in a flock of Merino wethers experimentally infected with footrot. The disease was allowed to spread freely amongst 150 of the flock but kept at very low prevalence in the remaining 50 by preventive footbathing during transmission periods. Severe, underrunning footrot had a significant adverse effect on body weight, for each year of the trial.
View Article and Find Full Text PDFDuring studies of flies that visit farm animals in north-east England, samples of Muscidae were obtained on a regular basis from grazing animals (mainly cattle) and from Manitoba traps. Female flies were examined to determine their wing length, degree of wing damage, whether or not they had mated, whether their crop or gut contained blood, the stage they had reached in ovarian development and the number of eggs present. This information was used to assess the timing of mating, the stage at which blood meals were taken and the potential fecundity of the more numerous species, especially Hydrotaea irritans (Fallén) and Morellia simplex (Loew).
View Article and Find Full Text PDF1. Some of the trap features influencing the ability of pitfall traps to catch Coleoptera, especially Carabidae, were investigated by field and laboratory experiments. 2.
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