Browsing by Subject "REACTIVITY"

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  • Weller, Stefan; Schlindwein, Simon H.; Feil, Christoph M.; Kelemen, Zsolt; Buzsaki, Daniel; Nyulaszi, Laszlo; Isenberg, Stefan; Pietschnig, Rudolf; Nieger, Martin; Gudat, Dietrich (2019)
    Reactions of P-chloro-1,3,2-diazaphospha[3]ferrocenophanes with ECl3 (E = Al, Ga) under solvent-free conditions and with Na[Mn(CO)(5)] furnished salts featuring a ferrocenophane-based phosphenium cation and neutral phosphenium complexes, respectively. All products were characterized by spectroscopic studies. Single-crystal X-ray diffraction studies confirmed the ionic nature of the phosphenium tetrachloroaluminate and the structural analogy between the phosphenium complexes and Fischer-type carbene complexes. Distinct deviations in the conformation of the ansa bridge suggest electronic stabilization of the electrophilic phosphorus atom by phosphorus-nitrogen pi interactions in the free cation and by phosphorus-metal pi bonding in the complexes. The observation of short intermolecular contacts in the crystalline phosphenium salt and its chemical behavior toward donor solvents attest to the cation having an unusually high degree of Lewis acidity, which was confirmed by DFT studies and related to the presence of a rather large N-P-N angle. Computational studies indicate further that the free phosphenium cation exhibits a closed-shell electronic structure with a formal Fe(II) oxidation state and is thus a true analogue to ferrocenophane-based diaminotetrylenes.
  • Acosta, H.; Tuulari, J. J.; Kantojärvi, K.; Lewis, J. D.; Hashempour, N.; Scheinin, N. M.; Lehtola, S. J.; Fonov, V. S.; Collins, D. L.; Evans, A.; Parkkola, R.; Lahdesmaki, T.; Saunavaara, J.; Merisaari, H.; Karlsson, L.; Paunio, T.; Karlsson, H. (2021)
    Genetic variants in the oxytocin receptor (OTR) have been linked to distinct social phenotypes, psychiatric disorders and brain volume alterations in adults. However, to date, it is unknown how OTR genotype shapes prenatal brain development and whether it interacts with maternal prenatal environmental risk factors on infant brain volumes. In 105 Finnish mother-infant dyads (44 female, 11-54 days old), the association of offspring OTR genotype rs53576 and its interaction with prenatal maternal anxiety (revised Symptom Checklist 90, gestational weeks 14, 24, 34) on infant bilateral amygdalar, hippocampal and caudate volumes were probed. A sex-specific main effect of rs53576 on infant left hippocampal volumes was observed. In boys compared to girls, left hippocampal volumes were significantly larger in GG-homozygotes compared to A-allele carriers. Furthermore, genotype rs53576 and prenatal maternal anxiety significantly interacted on right hippocampal volumes irrespective of sex. Higher maternal anxiety was associated both with larger hippocampal volumes in A allele carriers than GG-homozygotes, and, though statistically weak, also with smaller right caudate volumes in GG-homozygotes than A-allele carriers. Our study results suggest that OTR genotype enhances hippocampal neurogenesis in male GG-homozygotes. Further, prenatal maternal anxiety might induce brain alterations that render GG-homozygotes compared to A-allele carriers more vulnerable to depression.
  • Niittynen, Taru; Riihonen, Veera; Moscovice, Liza; Koski, Sonja (2022)
    Ensuring horse welfare is a central aim in equestrian activities. Training is an important context for welfare, as horses form long-lasting representations of people and actions at a young age. However, only a few studies have addressed horses' emotional responses during early training with humans. In this study, we followed N = 19 young horses, including naive yearlings and more experienced two-to three-year-olds, through five foundation training sessions over nine months. Our goal was to combine physiological and behavioral measures to assess emotional responses to early foundation training. Specifically, we measured salivary oxytocin (sOXT) in N = 100 samples and salivary cortisol (sCORT) in N = 96 samples before and after training sessions. We also recoded behavioral responses during training. Changes in sOXT during training predicted individual variation in behavioral responses: Horses who showed more affiliative human-directed behaviors during training had in-creases in sOXT, while horses who showed more behavioral indicators of discomfort during training had de-creases in sOXT. Salivary cortisol was not related to individual behavioral responses, but experienced horses had lower sCORT concentrations both before and after training, and all horses showed decreases in sCORT and in behaviors indicative of fear or discomfort as training progressed. In addition, sCORT increased during longer training sessions, consistent with the established role of cortisol in responding to physical stressors. We conclude that individual variation in positive or negative behavioral responses to foundation training corresponds with acute changes in sOXT concentrations in young horses, suggesting that sOXT may be useful as a non-invasive indicator of emotional responses in young horses.
  • Liebmann, Jonathan; Sobanski, Nicolas; Schuladen, Jan; Karu, Einar; Hellen, Heidi; Hakola, Hannele; Zha, Qiaozhi; Ehn, Mikael; Riva, Matthieu; Heikkinen, Liine; Williams, Jonathan; Fischer, Horst; Lelieyeld, Jos; Crowley, John N. (2019)
    The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (6 ANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O-3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49% of the local production rate of ANs, with contributions of 21 %, 18% and 12% for NO3, OH and O-3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.
  • Stadelmann, B.; Bender, J.; Förster, D.; Frey, W.; Nieger, M.; Gudat, D. (2015)
    A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)(4)]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 degrees C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)(4) complex. The different reaction products were characterized by spectral and XRD data. Computational studies indicate that the NHP units in all complexes display p-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre.
  • Sääksjärvi, Katri; Lehto, Elviira; Lehto, Reetta; Suhonen, Eira; Leppänen, Marja; Michels, Nathalie; Saha, Mari; Ray, Carola; Vepsäläinen, Henna; Pajulahti, Riikka; Heiman-Lindh, Anu; Sainio, Taina; Erkkola, Maijaliisa; Roos, Eva; Sajaniemi, Nina (2021)
    Associations between hair cortisol concentration (HCC), diurnal salivary cortisol (sCort) and alpha-amylase (sAA), and temperament dimensions were examined among 3-6-year-old Finnish children (n = 833). Children's hair samples were collected at preschool, while parents collected five saliva samples from children during one weekend day and completed a questionnaire assessing child's temperament dimensions i.e. surgency, negative affectivity, and effortful control (HCC, n = 677; AUCg of sAA, n = 380; AUCg of sCort, n = 302; temperament dimensions, n = 751). In linear regression analysis, diurnal sCort associated positively with HCC, the association persisting after adjustments (beta 0.31, 95% CI 0.20-0.42). In logistic regression analysis, increasing scores in effortful control associated with higher likelihood of having high HCC (OR 1.47, 95% CI 1.07-2.03), the association slightly attenuating to non-significant after adjustments. Otherwise, no clear indication for associations between temperament and stress-related biomarkers were found.
  • Borrega, Marc; Larsson, Per Tomas; Ahvenainen, Patrik; Ceccherini, Sara; Maloney, Thaddeus; Rautkari, Lauri; Sixta, Herbert (2018)
    Hydrothermal treatments of birch wood and kraft pulp were compared for their ability to extract the xylan and produce viscose-grade pulp. Water post-hydrolysis of kraft pulp produced a high-purity cellulosic pulp with lower viscosity but higher cellulose yield than traditional pre-hydrolysis kraft pulping of wood. Post-hydrolysis of pulp also increased the crystallite dimensions and degree of crystallinity in cellulose, and promoted a higher extent of fibril aggregation. The lower specific surface area in post-hydrolyzed pulps, derived from their larger fibril aggregates, decreased the accessibility of OH groups. However, this lower accessibility did not seem to decrease the pulp reactivity to derivatizing chemicals. In the aqueous side-stream, the xylose yield was similar in both pre- and post-hydrolysates, although conducting post-hydrolysis of pulp in a flow-through system enabled the recovery of high purity and molar mass (∼10 kDa) xylan for high-value applications.
  • Boom, Devin H. A.; de Boed, Ewoud J. J.; Nicolas, Emmanuel; Nieger, Martin; Ehlers, Andreas W.; Jupp, Andrew R.; Slootweg, J. Chris (2020)
    The reaction of the intramolecular frustrated Lewis pair (FLP) tBu2PCH2BPh2 with the amine-boranes NH3·BH3 and Me2NH·BH3 leads to the formation of the corresponding FLP-H2 adducts as well as novel five-membered heterocycles that result from capturing the in situ formed amino-borane by a second equivalent of FLP. The sterically more demanding tBu2PCH2BMes2 does not form such a five-membered heterocycle when reacted with Me2NH·BH3 and its H2 adduct liberates dihydrogen at elevated temperatures, promoting the metal-free catalytic dehydrogenation of amine-boranes.
  • Suhonen, Eira; Sajaniemi, Nina K.; Alijoki, Alisa; Nislin, Mari A. (2018)
    We aimed to investigate stress response regulation, temperament, cognitive and language abilities and family SES in children who entered kindergarten before two years of age. Whilst childrens stress regulatory systems are vulnerable to environmental influences little is known about how temperament and family characteristics impact on stress regulation in early years. Participants were 129 children (age 7 to 23 months) from 29 kindergartens. Stress response regulation was assessed by measuring salivary cortisol and alpha-amylase activity. Cognitive and language abilities were assessed using Bayley-III and children temperament with ECBQ-questionnaire. Family characteristics were assessed with surveys. Results suggest that children are alerted during kindergarten day, but their stress response regulation is balanced. Girls and boys differed in cognitive and language abilities. We propose that childrens individual needs should be better acknowledged in kindergartens.
  • Feil, Christoph M.; Hettich, Thomas D.; Beyer, Katharina; Sondermann, Christina; Schlindwein, Simon H.; Nieger, Martin; Gudat, Dietrich (2019)
    N-Heterocyclic phosphenium (NHP) and nitro-sonium (NO+) ligands are often viewed as isolobal analogues that share the capability to switch between different charge states and thus display redox "noninnocent" behavior. We report here on mixed complexes [(NHP)M(CO)(n)(NO)] (M = Fe, Cr; n = 2, 3), which permit evaluating the donor/acceptor properties of both types of ligands and their interplay in a single complex. The crystalline target compounds were obtained from reactions of N-heterocyclic phosphenium triflates with PPN[Fe(CO)(3)(NO)] or PPN[Cr(CO)(4)-(NO)], respectively, and fully characterized (PPN = nitride-bistriphenylphosphonium cation). The structural and spectroscopic (IR, UV-vis) data support the presence of carbene-analogue NHP ligands with an overall positive charge state and pi-acceptor character. Even if the structural features of the M-NO unit were in all but one product blurred by crystallographic CO/NO disorder, spectroscopic studies and the structural data of the remaining compound suggest that the NO units exhibit nitroxide (NO-) character. This assignment was validated by computational studies, which reveal also that the electronic structure of iron NHP/ NO complexes is closely akin to that of the Hieber anion, [Fe(CO)(3)(NO)](-). The electrophilic character of the NHP units is further reflected in the chemical behavior of the mixed complexes. Cyclic voltammetry and IR-SEC studies revealed that complex [(NHP)Fe(CO)(2) (NO)] (4) undergoes chemically reversible one-electron reduction. Computational studies indicate that the NHP unit in the resulting product carries significant radical character, and the reduction may thus be classified as predominantly ligand-centered. Reaction of 4 with sodium azide proceeded likewise under nucleophilic attack at phosphorus and decomplexation, while super hydride and methyl lithium reacted with all chromium and iron complexes via transfer of a hydride or methyl anion to the NHP unit to afford anionic phosphine complexes. Some of these species were isolated after cation exchange or trapped with electrophiles (H+, SnPh3(+)) to afford neutral complexes representing the products of a formal hydrogenation or hydrostannylation of the original M=P double bond.
  • Ronnberg, Bengt; Gustafsson, Ake; Vapalahti, Olli; Emmerich, Petra; Lundkvist, Ake; Schmidt-Chanasit, Jonas; Blomberg, Jonas (2017)
    The recent spread of Zika virus (ZIKV) in the Americas and Asia necessitates an increased preparedness for improved maternal and perinatal health and blood safety. However, serological cross-reactions, especially to Dengue virus (DENV), complicate ZIKV antibody serodiagnosis. A novel "pan-Flavi" suspension multiplex immunoassay (PFSMIA) using 25 antigens, whole virus (WV), non-structural protein 1 (NS1), and envelope (E) proteins, from 7 zoonotic flaviviruses for specific detection of ZIKV and DENV IgM and IgG was developed. Patterns of antibody cross-reactivity, avidity, and kinetics were established in 104 sera from returning travelers with known ZIKV and DENV infections. PFSMIA gave IgM- and IgG-sensitivities for both viruses of 96-100%, compared to an immunofluorescence assay. Main IgM cross-reactions were to NS1, for IgG to the E and WV antigens. Infecting virus yielded reactivity to several antigens of the homologous virus, while cross-reactions tended to occur only to a single antigen from heterologous virus(es). A specificity-enhancing computer procedure took into account antibody isotype, number of antibody-reactive antigens per virus, avidity, average degree of cross-reactivity to heterologous flavivirus antigens, and reactivity changes in serial sera. It classified all 50 cases correctly. Applied to sera from 200 pregnant women and 173 blood donors from Sweden, one blood donor was found ZIKV NS1 IgM positive, and another as ZIKV NS1 IgG positive. These samples did not react with other ZIKV antigens and were thereby judged as false-positives. PFSMIA provided sensitive and specific ZIKV and DENV serology, warranting high-throughput serological surveillance and a minimized need for laborious and expensive virus neutralization assays.
  • Tawfeek, Hendawy N.; Hassan, Alaa A.; Brase, S.; Nieger, M.; Mostafa, Yaser A.; Gomaa, Hesham A. M.; Youssif, Bahaa G. M.; El-Shreef, Essmat M. (2022)
    A series of novel thiazolidine-4-one derivatives was synthesized by reacting 1,4disubstituted hydrazine carbothioamides with diethyl azodicarboxylate. The structures were confirmed by spectroscopic data as well as single-crystal X-ray analyses. The antiproliferative activity of the synthesized compounds was investigated against four human cancer cell lines using an MTT assay. Compounds 5d, 5e, and 5f revealed the most potent antiproliferative activity with GI50 values ranging from 0.70 mM to 1.20 mM, compared to doxorubicin GI50 value = 1.10 mM. Compounds 5d, 5e, and 5f were further investigated for their inhibitory activities against CDK2 and EGFR as potential targets for their molecular mechanism. Compounds 5e and 5f have showed potent inhibitory activity to CDK2 enzyme with IC50 values of 18 and 14 nM, which is more potent than the reference dinaciclib (IC50 = 20 nM). Moreover, compounds 5e and 5f were the most potent EGFR inhibitors, with IC50 values of 93 and 87 nM, respectively, compared to the reference erlotinib (IC50 = 70 nM). In addition, the most potent derivatives were tested for their apoptotic activity against caspases 3, 8, and 9, and the results showed that compounds 5d, 5e, and 5f revealed a greater increase in active caspases 3,8 and 9 than doxorubicin. Also, compounds 5d, 5e, and 5f elevated cytochrome C levels in the MCF-7 human breast cancer cell line by about 15.5, 15.8, and 16.5 times, respectively. Finally, a molecular docking study was performed to investigate the binding sites of these compounds within the active sites of CDK2 and EGFR targets, and the results confirmed that the most potent CDK2 and EGFR inhibitor 5h also have showed the highest docking (c) 2022 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
  • Bhide, Amarnath; Alanne, Leena; Rasanen, Juha; Huhta, Heikki; Junno, Juulia; Kokki, Merja; Erkinaro, Tiina; Ohtonen, Pasi; Haapsamo, Mervi; Acharya, Ganesh (2019)
    Sildenafil is a potential new treatment for placental insufficiency in human pregnancies as it reduces the breakdown of vasodilator nitric oxide. Pulmonary vasodilatation is observed in normoxemic fetuses following sildenafil administration. Placental insufficiency often leads to fetal hypoxemia that can cause pulmonary vasoconstriction and fetal cardiac dysfunction as evidenced by reduced isovolumic myocardial velocities. We tested the hypotheses that sildenafil, when given directly to the hypoxemic fetus, reverses reactive pulmonary vasoconstriction, increases left ventricular cardiac output by increasing pulmonary venous return, and ameliorates hypoxemic myocardial dysfunction. We used an instrumented sheep model. Fetuses were made hypoxemic over a mean (standard deviation) duration of 41.3 (9.5) minutes and then given intravenous sildenafil or saline infusion. Volume blood flow through ductus arteriosus was measured with an ultrasonic transit-time flow probe. Fetal left and right ventricular outputs and lung volume blood flow were calculated, and ventricular function was examined using echocardiography. Lung volume blood flow decreased and the ductus arteriosus volume blood flow increased with hypoxemia. There was a significant reduction in left ventricular and combined cardiac outputs during hypoxemia in both groups. Hypoxemia led to a reduction in myocardial isovolumic velocities, increased ductus venosus pulsatility, and reduced left ventricular myocardial deformation. Direct administration of sildenafil to hypoxemic fetus did not reverse the redistribution of cardiac output. Furthermore, fetal cardiac systolic and diastolic dysfunction was observed during hypoxemia, which was not improved by fetal sildenafil treatment. In conclusion, sildenafil did not improve pulmonary blood flow or cardiac function in hypoxemic sheep fetuses.
  • Alanne, Leena; Bhide, Amarnath; Hoffren, Jonna; Lantto, Juulia; Huhta, Heikki; Kokki, Merja; Haapsamo, Mervi; Acharya, Ganesh; Räsänen, Juha (2020)
    Introduction We hypothesized that nifedipine and sildenafil would have no detrimental effects on placental hemodynamics and gas exchange under fetal hypoxemia. Methods In 33 chronically instrumented fetal sheep, placental volume blood flow (QPlac) and umbilical artery (UA) vascular impedance were measured by Doppler ultrasonography. Fetal carotid artery blood pressure and blood gas values were monitored. After baseline data collection, maternal and fetal hypoxemia were induced. Following hypoxemia phase data collection, 12 fetuses received sildenafil and 9 fetuses nifedipine infusion, and 12 fetuses served as controls receiving saline infusion. Data were collected 30 and 120 min after infusion was started. Then maternal oxygenation was normalized and normoxemia phase data were collected, while infusion was continued. Results Hypoxemia significantly decreased fetal pO2 and blood pressure. In the sildenafil group at 30- and 120-min hypoxemia + infusion phases, fetal blood pressure and QPlac were significantly lower and pCO2 higher than at baseline without returning to baseline level at normoxemia + infusion phase. In hypoxemia, nifedipine did not affect fetal blood pressure or placental hemodynamics. Both in the sildenafil and nifedipine groups, fetal pO2 remained significantly lower at normoxemia + infusion phase than in the control group. Umbilical artery vascular impedance did not change during the experiment. Discussion In fetal hypoxemia, sildenafil had detrimental effects on placental hemodynamics that disturbed placental gas exchange. Nifedipine did not alter placental hemodynamics in hypoxemia but disturbed placental gas exchange upon returning to normoxemia. Umbilical artery vascular impedance did not reflect alterations in placental hemodynamics.
  • Uotila, Riikka; Röntynen, Petteri; Pelkonen, Anna S.; Voutilainen, Helena; Kaarina Kukkonen, Anna; Mäkelä, Mika J. (2020)
  • Boom, Devin H. A.; Ehlers, Andreas W.; Nieger, Martin; Devillard, Marc; Bouhadir, Ghenwa; Bourissou, Didier; Slootweg, J. Chris (2018)
    In this work, we explored the coordination properties of the geminal phosphinoborane tBu(2)PCH(2)BPh(2) (2) toward different gold(I) precursors. The reaction of 2 with an equimolar amount of the sulfur-based complex (Me2S) AuCl resulted in displacement of the SMe2 ligand and formation of linear phosphine gold(I) chloride 3. Using an excess of ligand 2, bisligated complex 4 was formed and showed dynamic behavior at room temperature. Changing the gold(I) metal precursor to the phosphorus-based complex, (Ph3P) AuCl impacted the coordination behavior of ligand 2. Namely, the reaction of ligand 2 with (Ph3P) AuCl led to the heterolytic cleavage of the gold-chloride bond, which is favored over PPh3 ligand displacement. To the best of our knowledge, 2 is the first example of a P/Bambiphilic ligand capable of cleaving the gold-chloride bond. The coordination chemistry of 2 was further analyzed by density functional theory calculations.
  • Bowden, Mark E.; Ginovska, Bojana; Jones, Martin Owen; Karkamkar, Abhijeet J.; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.; Schenter, Gregory K.; Miller, Seth A.; Repo, Timo; Chernichenko, Konstantin; Leick, Noemi; Martinez, Madison B.; Autrey, Tom (2020)
    We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis (pentafluorophenyOboryl] phenyl -2, 2,6,6-tetrame-thylpiperidine (KCAT). The gas-solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H-2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4-200 K did not provide evidence for the formation of polarized H-2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H-2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H-2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H-2 diffusion into the FLP crystal with a rate-limiting movement of H-2 from inactive positions to reactive sites.
  • PLATO Investigators; Franchi, Francesco; James, Stefan K.; Lakic, Tatevik Ghukasyan; Lassila, Riitta (2019)
    Background-There are limited data on how the combination of diabetes mellitus (DM) and chronic kidney disease (CKD) affects cardiovascular outcomes as well as response to different P2Y(12) receptor antagonists, which represented the aim of the present investigation. Methods and Results-In this post hoc analysis of the PLATO (Platelet Inhibition and Patient Outcomes) trial, which randomized acute coronary syndrome patients to ticagrelor versus clopidogrel, patients (n=15 108) with available DM and CKD status were classified into 4 groups: DM+/CKD+ (n=1058), DM+/CKD- (n=2748), DM-/CKD+ (n=2160), and DM-/CKD- (n=9142). The primary efficacy end point was a composite of cardiovascular death, myocardial infarction, or stroke at 12 months. The primary safety end point was PLATO major bleeding. DM+/CKD+ patients had a higher incidence of the primary end point compared with DM-/CKD- patients (23.3% versus 7.1%; adjusted hazard ratio 2.22; 95% CI 1.88-2.63; P Conclusions-In acute coronary syndrome patients, a gradient of risk was observed according to the presence or absence of DM and CKD, with patients having both risk factors at the highest risk. Although the ischemic benefit of ticagrelor over clopidogrel was consistent in all subgroups, the absolute risk reduction was greatest in patients with both DM and CKD.
  • Valoppi, Fabio; Haman, Nabil; Ferrentino, Giovanna; Scampicchio, Matteo (2020)
    This study aims to evaluate the effect of vegetable waxes on the kinetics of lipid oxidation of linseed oil. Apple and orange waxes were obtained using supercritical carbon dioxide. The capacity of waxes to inhibit or retard the oxidation of linseed oil was determined by isothermal calorimetry at 298 K. The results show that waxes were able to slow down linseed oil autoxidation, with apple waxes being more active than orange waxes. However, such activity was visible only at relatively high concentrations (>1% of waxes), greatly higher than the concentration used with radical chain breakers like BHT (0.2%). The inhibition activity was explained by considering three different mechanisms: (1) residual polyphenol content in the wax, (2) high termination rate of the radical chain process, and (3) physical hindrance of the oxidation process by change in viscosity. All these mechanisms were possible, although the latter seemed to be the most important. Finally, the importance of waxes in the inhibition of lipid autoxidation was determined by testing their inhibition activity in combination with primary antioxidants. A mixture of waxes with BHA, ethoxyquin and alpha-tocopherol showed a higher rate of inhibition than when present individually. This suggested a strong cooperative radical scavenging activity, whose beneficial effect might pave the way to the formulation of novel functional ingredients.