Husumgibbs9752

Dissociative tunneling ionization of tetrafluoromethane (CF4) in circularly polarized ultrashort intense laser fields (35 fs, 0.8 × 1014 W cm-2, 1035 nm), CF4 → CF4+ + e- → CF3+ + F + e-, has been studied by three-dimensional electron-ion coincidence momentum imaging. The photoelectron angular distribution in the recoil frame revealed that the dissociative tunneling ionization occurs efficiently when the laser electric field points from F to C. The obtained results are qualitatively consistent with the theoretical predictions by the weak-field asymptotic theory (WFAT) for tunneling ionization from the highest and next-highest occupied molecular orbitals, HOMO (1t1), and HOMO-1 (4t2), respectively. On the other hand, the angular distribution shows clear dependences on the polarization helicity, indicating that the breaking of the C-F bonds is sensitive to the helicity of the multicycle circularly polarized laser fields.The new experimental value of 13C absolute shielding constant in an isolated 13CO molecule was evaluated from the 13C and 3He gas phase NMR measurements performed for 3He/13CO mixtures. An absolute shielding constant σ0(13CO)300 K= 0.80(90) ppm was previously formally established for this reference molecule with uncertainty but much higher precision than ever before. This result serves as a reference value for the 13C NMR absolute shielding scale. Several earlier used shielding values were noted and then discussed. Taking this estimate into account, we also report the gas-phase 13C shielding constants obtained by extrapolation to the zero density limit for 57 carbon containing molecules and 86 different atom positions in the molecules. Our results are very precise experimental absolute shielding values which are a benchmark set of data suitable for comparison with the sophisticated theoretical calculations. They fully correlate with the experimental and advanced theoretical values reported earlier in the literature. The shielding constant of tetramethylsilane (TMS) of neat liquid used as an external standard is established as σ(13C)300 K(TMS) = 186.43(90) ppm. For TMS used as internal standard, σ(13C)300 K(0.05% TMS in CDCl3) = 186.43 + 0.048(%) ppm and this value can be recommended as a secondary reference. With more than 20 years of achievements in this field, we report a large collection of carbon shielding constants and second virial coefficients from the gas phase experiments.The synthesis and reactivity of novel ferrocene tethered boramidinate frustrated Lewis pairs (FLPs), capable of the sequential capture of small molecules, is reported. Reactions of 1,1'-dicarbodiimidoferrocenes with different boranes provides access to metallocene tethered FLPs. The reactivity of the boramidinate moieties can be tuned by the nature of the carbodiimido substituents (alkyl vs. aryl) and the borane used in the reduction (9-borabicyclo[3.3.1]nonane [(C8H14)2BH]2vs. bis-pentafluorophenyl borane [(C6F5)2BH]2). The boramidinate FLP arms do not engage in intramolecular reactions, allowing for independent small molecule capture by each FLP. By careful synthetic control, sequential capture of different gaseous small molecules (CO2 and CO or CO2 and CNtBu) by the same bis(boramidinate)ferrocene molecule has been demonstrated.Vitamin D deficiency is a global health issue with consequences for bone health. Complexation of vitamin D3 with specific whey proteins might increase the bioavailability and enhance the effect of dietary supplementation on health outcomes. The current rat study was set up to investigate if complexation of vitamin D3 with whey protein isolate (WPI) or β-lactoglobulin (B-LG) increases bioavailability of the vitamin and how it impacts markers of bone turnover and bone structure. For 8 weeks, growing male Sprague Dawley rats (n = 48) were fed a vitamin D-deficient diet and during the final 4 weeks gavage dosing of vitamin D3 either alone (VitD) or complexed with WPI (VitD + WPI) or β-LG (VitD + B-LG) was administered. A placebo treatment (placebo) was also included. After sacrifice, samples of bone were collected and analyzed using biomechanical testing and μCT scanning. The concentrations of vitamin D3, vitamin D3 metabolites and bone markers (P1NP and CTX) were measured in serum. The results showed that VitD + B-LG appeared to induce lower levels of 25-hydroxy vitamin D3 in serum compared to VitD alone. Markers of bone turnover were generally higher in the VitD group compared to placebo and the VitD + WPI and VitD + B-LG treatments. No effects of treatments on bone strength or bone microstructure were detected. In conclusion, whey protein complexation of vitamin D3 supplements appeared to have no beneficial effects on circulating vitamin D3 metabolites but this did not impose changes in bone strength or trabecular bone microstructure.

As-needed intranasal corticosteroid spray (INCS) is commonly used by patients with allergic rhinitis (AR) who have suboptimal symptom control. This systematic review aimed to assess the effectiveness of as-needed INCS for treating AR.

Systematic searches for randomized controlled trials studying the effects of as-needed INCS compared to regular INCS, as-needed antihistamine, or placebo were performed. Primary outcomes were total nasal symptom score (TNSS) and disease-specific quality of life (DSQoL).

Eight studies (882 participants) met the criteria. Regular use of INCS showed greater improvements than as-needed INCS in TNSS, DSQoL, nasal peak inspiratory flow, sneezing, and nasal congestion scores with small effect sizes. https://www.selleckchem.com/products/etomoxir-na-salt.html There were no differences between regular and as-needed INCS usage for ocular symptoms, symptom-free days, nasal itching, and rhinorrhea scores. As-needed INCS was superior to as-needed antihistamine and placebo with medium effect sizes. There were no differences in risk of adverse events between the groups in all three comparisons.

Regular use of INCS improved total nasal symptoms score and DSQoL better than as-needed INCS. However, as-needed INCS improved TNSS better than as-needed antihistamine and placebo. The effects of as-needed INCS were closer to regular INCS usage than to placebo or as-needed AH usage.

Regular use of INCS improved total nasal symptoms score and DSQoL better than as-needed INCS. However, as-needed INCS improved TNSS better than as-needed antihistamine and placebo. The effects of as-needed INCS were closer to regular INCS usage than to placebo or as-needed AH usage.

Changes in the nasal function following total laryngectomy resulted in histopathological alterations of the nasal mucosa. We aimed to evaluate the long-term histopathological changes and the mucociliary clearance (MCC) of the nasal mucosa after total laryngectomy.

We performed a histological examination of inferior turbinate biopsy, and saccharine test to assess the MCC time for patients who were candidates for total laryngectomy before the procedure, 6-12 months after surgery, and at least two years postoperatively.

Seventy-five patients scheduled for total laryngectomy were initially enrolled in our study. We excluded patients who received postoperative radiotherapy or were lost during the follow-up period. Eventually, 63 and 54 patients were available for assessment 6-12 months after surgery and at least two years postoperatively, respectively. Except for ciliary and goblet cell destruction, which were significantly reduced 6-12 months postoperatively, there were no statistically significant differences in the histopathological findings of the nasal mucosa before surgery and 6-12 months postoperatively. After two years, the histopathological alterations of the nasal mucosa were statistically more evident than those before surgery and 6-12 months postoperatively; the most common histopathological findings were mononuclear cell infiltration and stromal fibrosis. The mean MCC time preoperatively was 12.56 minutes that statistically significantly decreased to 11.81 minutes 6-12 months after surgery; then, it significantly increased to 20.98 minutes at least two years postoperatively.

After total laryngectomy, the nasal mucosa showed histopathological alterations and early enhancement of the MCC, which was later impaired due to nasal mucosal atrophy and the saprophytic infection.

After total laryngectomy, the nasal mucosa showed histopathological alterations and early enhancement of the MCC, which was later impaired due to nasal mucosal atrophy and the saprophytic infection.Hydrocephalus, characterized by cerebral ventricular dilatation, is routinely attributed to primary defects in cerebrospinal fluid (CSF) homeostasis. This fosters CSF shunting as the leading reason for brain surgery in children despite considerable disease heterogeneity. In this study, by integrating human brain transcriptomics with whole-exome sequencing of 483 patients with congenital hydrocephalus (CH), we found convergence of CH risk genes in embryonic neuroepithelial stem cells. Of all CH risk genes, TRIM71/lin-41 harbors the most de novo mutations and is most specifically expressed in neuroepithelial cells. Mice harboring neuroepithelial cell-specific Trim71 deletion or CH-specific Trim71 mutation exhibit prenatal hydrocephalus. CH mutations disrupt TRIM71 binding to its RNA targets, causing premature neuroepithelial cell differentiation and reduced neurogenesis. Cortical hypoplasia leads to a hypercompliant cortex and secondary ventricular enlargement without primary defects in CSF circulation. These data highlight the importance of precisely regulated neuroepithelial cell fate for normal brain-CSF biomechanics and support a clinically relevant neuroprogenitor-based paradigm of CH.The age at onset of motor symptoms in Huntington's disease (HD) is driven by HTT CAG repeat length but modified by other genes. In this study, we used exome sequencing of 683 patients with HD with extremes of onset or phenotype relative to CAG length to identify rare variants associated with clinical effect. We discovered damaging coding variants in candidate modifier genes identified in previous genome-wide association studies associated with altered HD onset or severity. Variants in FAN1 clustered in its DNA-binding and nuclease domains and were associated predominantly with earlier-onset HD. Nuclease activities of purified variants in vitro correlated with residual age at motor onset of HD. Mutating endogenous FAN1 to a nuclease-inactive form in an induced pluripotent stem cell model of HD led to rates of CAG expansion similar to those observed with complete FAN1 knockout. Together, these data implicate FAN1 nuclease activity in slowing somatic repeat expansion and hence onset of HD.Characterization of the genetic landscape of Alzheimer's disease (AD) and related dementias (ADD) provides a unique opportunity for a better understanding of the associated pathophysiological processes. We performed a two-stage genome-wide association study totaling 111,326 clinically diagnosed/'proxy' AD cases and 677,663 controls. We found 75 risk loci, of which 42 were new at the time of analysis. Pathway enrichment analyses confirmed the involvement of amyloid/tau pathways and highlighted microglia implication. Gene prioritization in the new loci identified 31 genes that were suggestive of new genetically associated processes, including the tumor necrosis factor alpha pathway through the linear ubiquitin chain assembly complex. We also built a new genetic risk score associated with the risk of future AD/dementia or progression from mild cognitive impairment to AD/dementia. The improvement in prediction led to a 1.6- to 1.9-fold increase in AD risk from the lowest to the highest decile, in addition to effects of age and the APOE ε4 allele.