Monometallic Ni, Pd and Pt and bimetallic catalysts formed by combinations of the above metals supported on SBA-15 silica were synthesized, characterized and tested in the hydrodeoxygenation reaction ...of anisole. The objective of the work was to detect the effect of the nature of metals on the activity of the catalysts at different steps of anisole hydrodeoxygenation: hydrogenation of the aromatic ring of anisole and C-O bond cleavage in the intermediate cyclohexyl methyl ether. The support and the catalysts were characterized by N
2
physisorption, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and HAADF-STEM. The catalytic activity tests were carried out in a batch reactor at 280 °C and 7.3 MPa pressure. The activity results show that the NiPd/SBA-15 catalyst had the greatest ability for hydrogenation of the aromatic ring of anisole, while its NiPt/SBA-15 analog resulted in better activity for C-O bond hydrogenolysis. The bimetallic NiPt/SBA-15 catalyst showed the best catalytic performance in the HDO of anisole ascribed to the formation of a Ni-Pt alloy. On the other hand, the combination of Pd and Pt metals in the PdPt/SBA-15 catalyst resulted in the formation of bimetallic particles with Pd-rich and Pt-rich domains, showing high selectivity for the formation of the cyclohexyl methyl ether, which can be useful for the hydrogenation of aromatic rings in O-containing reactants with the formation of saturated O-containing products. According to the characterization results (HAADF-STEM), the different catalytic behavior of NiPd/SBA-15, NiPt/SBA-15, and PdPt/SBA-15 catalysts could be attributed to different characteristics of the bimetallic active phases in them.
NiPt/SBA-15 and NiPd/SBA-15 catalysts were active for hydrodeoxygenation of anisole to cyclohexane, while PdPt/SBA-15 was active for hydrogenation of anisole to cyclohexyl methyl ether.
Saliva is a promising specimen for the detection of viruses that cause upper respiratory infections including severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) due to its ...cost‐effectiveness and noninvasive collection. However, together with intrinsic enzymes and oral microbiota, children's unique dietary habits may introduce substances that interfere with diagnostic testing. To determine whether children's dietary choices impact SARS‐CoV‐2 molecular detection in saliva, we performed a diagnostic study that simulates testing of real‐life specimens provided from healthy children (n = 5) who self‐collected saliva at home before and at 0, 20, and 60 min after eating 20 foods they selected. Each of 72 specimens was split into two volumes and spiked with SARS‐CoV‐2‐negative or SARS‐CoV‐2‐positive clinical standards before side‐by‐side testing by reverse‐transcription polymerase chain reaction matrix‐assisted laser desorption ionization time‐of‐flight (RT‐PCR/MALDI‐TOF) assay. Detection of internal extraction control and SARS‐CoV‐2 nucleic acids was reduced in replicates of saliva collected at 0 min after eating 11 of 20 foods. Interference resolved at 20 and 60 min after eating all foods except hot dogs in one participant. This represented a significant improvement in the detection of nucleic acids compared to saliva collected at 0 min after eating (p = 0.0005). We demonstrate successful detection of viral nucleic acids in saliva self‐collected by children before and after eating a variety of foods. Fasting is not required before saliva collection for SARS‐CoV‐2 testing by RT‐PCR/MALDI‐TOF, but waiting for 20 min after eating is sufficient for accurate testing. These findings should be considered for SARS‐CoV‐2 testing and broader viral diagnostics in saliva specimens.
Highlights
Inconsistent collection and dietary habits impact viral nucleic acid detection in saliva.
Various foods interfere with severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) detection in saliva self‐collected by children.
Waiting 20 min after eating is sufficient for accurate SARS‐CoV‐2 testing in saliva.
Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride–trifluoroethylene) copolymer. Although this ...copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.
Thin films of polymeric blends composed of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polyethylene oxide (PEO) were investigated by varying the concentration of the two ...components over the entire range of compositions and the molecular weight of PEO. Phase separation and crystallization have been studied at different length scales by combining Atomic Force Microscopy (AFM) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) using synchrotron light. Several different arrangements in the thin films of the two polymers constituting the blend were observed and discussed in detail, providing information about their reciprocal influence at the micro- and nano-scale. In addition to that, we were able to estimate quantitative nanomechanical and nanoelectrical properties via AFM and finally revealing the dependence of the thin films' physical properties on their composition and structure. By varying the blend composition, we achieved different coating capability, mechanical properties, and electrical conductivity. Furthermore, depending on the PEO molecular weight, the electrical response of the resulting blends’ thin films shows some differences. In the low range concentration, the blend thin films with high molecular weight PEO present coarser conducting paths than in those with the low molecular weight counterparts. For intermediate concentrations, a more effective phase segregation of PEDOT:PSS and PEO is achieved for high molecular weight PEO. These differences are also translated to different electrical conductivity.
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•Thin films of PEDOT:PSS/PEO blends show different complex arrangements at the micro and nano-scale.•PEO improves the coating capability of PEDOT:PSS.•Phase separation and crystallization have been studied at different length scales.•Mechanical and electrical properties are related to the fraction of PEO and to its molecular weight.
Several components of the Wnt signaling cascade have been shown to function either as tumor suppressor proteins or as oncogenes in multiple human cancers, underscoring the relevance of this pathway ...in oncogenesis and the need for further investigation of Wnt signaling components as potential targets for cancer therapy. Here, using expression profiling analysis as well as in vitro and in vivo functional studies, we show that the Wnt pathway component BCL9 is a novel oncogene that is aberrantly expressed in human multiple myeloma as well as colon carcinoma. We show that BCL9 enhances beta-catenin-mediated transcriptional activity regardless of the mutational status of the Wnt signaling components and increases cell proliferation, migration, invasion, and the metastatic potential of tumor cells by promoting loss of epithelial and gain of mesenchymal-like phenotype. Most importantly, BCL9 knockdown significantly increased the survival of xenograft mouse models of cancer by reducing tumor load, metastasis, and host angiogenesis through down-regulation of c-Myc, cyclin D1, CD44, and vascular endothelial growth factor expression by tumor cells. Together, these findings suggest that deregulation of BCL9 is an important contributing factor to tumor progression. The pleiotropic roles of BCL9 reported in this study underscore its value as a drug target for therapeutic intervention in several malignancies associated with aberrant Wnt signaling.
The phase diagram of water harbors controversial views on underlying structural properties of its constituting molecular moieties, its fluctuating hydrogen-bonding network, as well as ...pair-correlation functions. In this work, long energy-range detection of the X-ray absorption allows us to unambiguously calibrate the spectra for water gas, liquid, and ice by the experimental atomic ionization cross-section. In liquid water, we extract the mean value of 1.74 ± 2.1% donated and accepted hydrogen bonds per molecule, pointing to a continuousdistribution model. In addition, resonant inelastic X-ray scattering with unprecedented energy resolution also supports continuous distribution of molecular neighborhoods within liquid water, as do X-ray emission spectra once the femtosecond scattering duration and proton dynamics in resonant X-ray–matter interaction are taken into account. Thus, X-ray spectra of liquid water in ambient conditions can be understood without a two-structure model, whereas the occurrence of nanoscalelength correlations within the continuous distribution remains open.
Plasmodium falciparum
malaria remains a devastating public health problem. Recent discoveries have shed light on the origin and evolution of
Plasmodium
parasites and their interactions with their ...vertebrate and mosquito hosts.
P. falciparum
malaria originated in Africa from a single horizontal transfer between an infected gorilla and a human, and became global as the result of human migration. Today,
P. falciparum
malaria is transmitted worldwide by more than 70 different anopheline mosquito species. Recent studies indicate that the mosquito immune system can be a barrier to malaria transmission and that the
P. falciparum Pfs47
gene allows the parasite to evade mosquito immune detection. Here, we review the origin and globalization of
P. falciparum
and integrate this history with analysis of the biology, evolution, and dispersal of the main mosquito vectors. This new perspective broadens our understanding of
P. falciparum
population structure and the dispersal of important parasite genetic traits.
Glial support is critical for normal axon function and can become dysregulated in white matter (WM) disease. In humans, loss-of-function mutations of
which encodes the inward-rectifying potassium ...channel KIR4.1, causes seizures and progressive neurological decline. We investigated Kir4.1 functions in oligodendrocytes (OLs) during development, adulthood and after WM injury. We observed that Kir4.1 channels localized to perinodal areas and the inner myelin tongue, suggesting roles in juxta-axonal K
removal. Conditional knockout (cKO) of OL-
resulted in late onset mitochondrial damage and axonal degeneration. This was accompanied by neuronal loss and neuro-axonal dysfunction in adult OL-
cKO mice as shown by delayed visual evoked potentials, inner retinal thinning and progressive motor deficits. Axon pathologies in OL-
cKO were exacerbated after WM injury in the spinal cord. Our findings point towards a critical role of OL-Kir4.1 for long-term maintenance of axonal function and integrity during adulthood and after WM injury.
High-throughput proteomic profiling using antibody or aptamer-based affinity reagents is used increasingly in human studies. However, direct analyses to address the relative strengths and weaknesses ...of these platforms are lacking. We assessed findings from the SomaScan1.3K (
= 1301 reagents), the SomaScan5K platform (
= 4979 reagents), and the Olink Explore (
= 1472 reagents) profiling techniques in 568 adults from the Jackson Heart Study and 219 participants in the HERITAGE Family Study across four performance domains: precision, accuracy, analytic breadth, and phenotypic associations leveraging detailed clinical phenotyping and genetic data. Across these studies, we show evidence supporting more reliable protein target specificity and a higher number of phenotypic associations for the Olink platform, while the Soma platforms benefit from greater measurement precision and analytic breadth across the proteome.
Immunotherapy with checkpoint inhibitors targeting the PD-1 (programmed cell death 1) axis has brought notable progress in patients with non-small cell lung cancer (NSCLC) and other cancers. However, ...autoimmune toxic effects are frequent and poorly understood, making it important to understand the pathophysiologic processes of autoimmune adverse effects induced by checkpoint inhibitor therapy.
To gain mechanistic insight into autoimmune skin toxic effects induced by anti-PD-1 treatment in patients with non-small cell lung cancer.
This prospective cohort study was conducted from July 1, 2016, to December 31, 2018. Patients (n = 73) with non-small cell lung cancer who received anti-PD-1 therapy (nivolumab or pembrolizumab) were recruited from 4 different centers in Switzerland (Kantonsspital St Gallen, Spital Grabs, Spital Wil, and Spital Flawil). Peripheral blood mononuclear cells, tumor biopsy specimens and biopsies from sites of autoimmune skin toxic effects were collected over a 2-year period, with patient follow-up after 1 year.
Response to treatment, overall survival, progression-free survival, and development of autoimmune toxic effects (based on standard laboratory values and clinical examinations).
Of the cohort of 73 patients with NSCLC (mean SD age, 68.1 8.9 years; 44 60% men), 25 (34.2% 95% CI, 24.4%-45.7%) developed autoimmune skin toxic effects, which were more frequent in patients with complete remission or partial remission (68.2% 95% CI, 47.3%-83.6%) than those with progressive or stable disease (19.6% 95% CI, 11.0%-32.5%) (χ2 = 14.02, P < .001). Nine T-cell antigens shared between tumor tissue and skin were identified. These antigens were able to stimulate CD8+ and CD4+ T cells in vitro. Several of the antigen-specific T cells found in blood samples were also present in autoimmune skin lesions and lung tumors of patients who responded to anti-PD-1 therapy.
These findings highlight a potential mechanism of checkpoint inhibitor-mediated autoimmune toxic effects and describe the association between toxic effects and response to therapy; such an understanding will help in controlling adverse effects, deciphering new cancer antigens, and further improving immunotherapy.
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