Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization

The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed

ESR evidence for disordered magnetic phase from ultra-small carbon nanotubes embedded in zeolite nanochannels

A multi-frequency electron spin resonance (ESR) study provides evidence for the occurrence of low temperature ferromagnetic/spin-glass behavior in aligned arrays of sub-nanometer single walled carbon nanotubes confined in zeolite nano-channels, owing to sp2-type non-bonding carbon associated localized states with density of ~3 x 1019 /g. Features related to the much anticipated conduction ESR are not detected. In the paramagnetic phase, the ESR linewidth is found to be weakly dependent on microwave frequency.Comment: Accepted to be published in EuroPhysics Letter

β-delayed fission and α decay of At196

A nuclear-decay spectroscopy study of the neutron-deficient isotope At196 is reported where an isotopically pure beam was produced using the selective Resonance Ionization Laser Ion Source and On-Line Isotope Mass Separator (CERN). The fine-structure α decay of At196 allowed the low-energy excited states in the daughter nucleus Bi192 to be investigated. A β-delayed fission study of At196 was also performed. A mixture of symmetric and asymmetric fission-fragment mass distributions of the daughter isotope Po196 (populated by β decay of At196) was deduced based on the measured fission-fragment energies. A βDF probability PβDF(At196)=9(1)×10−5 was determined

Ebstein’s anomaly may be caused by mutations in the sarcomere protein gene MYH7

Ebstein's anomaly is a rare congenital heart malformation characterised by adherence of the septal and posterior leaflets of the tricuspid valve to the underlying myocardium. Associated abnormalities of left ventricular morphology and function including left ventricular noncompaction (LVNC) have been observed. An association between Ebstein's anomaly with LVNC and mutations in the sarcomeric protein gene MYH7, encoding β-myosin heavy chain, has been shown by recent studies. This might represent a specific subtype of Ebstein's anomaly with a Mendelian inheritance pattern. In this review we discuss the association of MYH7 mutations with Ebstein's anomaly and LVNC and its implications for the clinical care for patients and their family members.Congenital Heart Diseas

Ruthenium indenylidene complexes bearing N-alkyl/N-mesityl-substituted N-heterocyclic carbene ligands

We report on the synthesis and characterization of second generation ruthenium indenylidene catalysts bearing unsymmetrical N-heterocyclic carbene (NHC) ligands denoted as RuCl2(3-phenyl-1-indenylidene)(1-mesityl-3-R-4,5-dihydroimidazol-2-ylidene)(PCy3), in which R is methyl 8a, octyl 8b or cyclohexyl 8c. The characterization of 8a-c was performed by NMR spectroscopy, elemental analysis, IR, HRMS and single-crystal X-ray diffraction analysis. In addition, the catalytic activity of the obtained initiators was evaluated in various representative metathesis reactions. The results reveal that the complexes 8a-c, bearing an N-alkyl side on the NHC, show a faster catalytic initiation than the reference complex 2. Complex 8a, which performs the best among the investigated indenylidene complexes, exhibits slower initiation but better overall efficiency than its benzylidene analogue 1c, especially in a low catalyst loading

Charge radii and electromagnetic moments of 195-211At

Hyperfine-structure parameters and isotope shifts of At195-211 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α-decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At197,199, for which a significant difference in the charge radii for ground (9/2-) and isomeric (1/2+) states has been observed

Enhanced Botrytis cinerea resistance of Arabidopsis plants grown in compost may be explained by increased expression of defense-related genes, as revealed by microarray analysis

Composts are the products obtained after the aerobic degradation of different types of organic matter waste and can be used as substrates or substrate/soil amendments for plant cultivation. There is a small but increasing number of reports that suggest that foliar diseases may be reduced when using compost, rather than standard substrates, as growing medium. The purpose of this study was to examine the gene expression alteration produced by the compost to gain knowledge of the mechanisms involved in compost-induced systemic resistance. A compost from olive marc and olive tree leaves was able to induce resistance against Botrytis cinerea in Arabidopsis, unlike the standard substrate, perlite. Microarray analyses revealed that 178 genes were differently expressed, with a fold change cut-off of 1, of which 155 were up-regulated and 23 were down-regulated in compost-grown, as against perlite-grown plants. A functional enrichment study of up-regulated genes revealed that 38 Gene Ontology terms were significantly enriched. Response to stress, biotic stimulus, other organism, bacterium, fungus, chemical and abiotic stimulus, SA and ABA stimulus, oxidative stress, water, temperature and cold were significantly enriched, as were immune and defense responses, systemic acquired resistance, secondary metabolic process and oxireductase activity. Interestingly, PR1 expression, which was equally enhanced by growing the plants in compost and by B. cinerea inoculation, was further boosted in compost-grown pathogen-inoculated plants. Compost triggered a plant response that shares similarities with both systemic acquired resistance and ABA-dependent/independent abiotic stress responses

Perceived responsiveness in suicidal ideation: An experience sampling study in psychiatric patients

Introduction: Perceived responsiveness, or the extent to which one feels understood, validated and cared for by close others, plays a crucial role in people's well‐being. Can this interpersonal process also protect people at risk? We assessed whether fluctuations in suicidal ideation were associated with fluctuations in the degree of perceived responsiveness that psychiatric patients (admitted in the context of suicide or indicating suicidal ideation) experienced in daily interactions immediately after discharge. Methods: Fifty‐seven patients reported on suicidal ideation (5 times a day) and perceived responsiveness (daily) for four consecutive weeks. The effects of established risk factors—thwarted belongingness, perceived burdensomeness, and hopelessness—were assessed as well. Results: The more patients felt that close others had been responsive to them, the less suicidal ideation they reported. At low levels of thwarted belongingness, perceived burdensomeness, or hopelessness, perceived responsiveness seemed to play a protective role, negatively co‐occurring with suicidal ideation. When thwarted belongingness, perceived burdensomeness, and hopelessness were high, perceived responsiveness did not have an effect. Conclusion: Perceived responsiveness could be a protective factor for suicidal ideation for people at risk only when they are experiencing low levels of negative perceptions. When experiencing highly negative perceptions, however, perceived responsiveness seems to matter less

The relationship between fractional flow reserve, platelet reactivity and platelet leukocyte complexes in stable coronary artery disease

Background: The presence of stenoses that significantly impair blood flow and cause myocardial ischemia negatively affects prognosis of patients with stable coronary artery disease. Altered platelet reactivity has been associated with impaired prognosis of stable coronary artery disease. Platelets are activated and form complexes with leukocytes in response to microshear gradients caused by friction forces on the arterial wall or flow separation. We hypothesized that the presence of significantly flow-limiting stenoses is associated with altered platelet reactivity and formation of platelet-leukocyte complexes. Methods: One hundred patients with stable angina were studied. Hemodynamic significance of all coronary stenoses was assessed with Fractional Flow Reserve (FFR). Patients were classified FFR-positive (at least one lesion with FFR 0.80). Whole blood samples were stimulated with increasing concentrations of ADP, TRAP, CRP and Iloprost with substimulatory ADP. Expression of P-selectin as platelet activation marker and platelet-leukocyte complexes were measured by flowcytometry. Patients were stratified on clopidogrel use. FFR positive and negative patient groups were compared on platelet reactivity and platelet-leukocyte complexes. Results: Platelet reactivity between FFR-positive patients and FFR-negative patients did not differ. A significantly lower percentage of circulating platelet-neutrophil complexes in FFR-positive patients and a similar non-significant decrease in percentage of circulating platelet-monocyte complexes in FFR-positive patients was observed. Conclusion: The presence of hemodynamically significant coronary stenoses does not alter platelet reactivity but is associated with reduced platelet-neutrophil complexes in peripheral blood of patients with stable coronary artery disease