The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby ...obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis.
We report the operation of a cold-atom inertial sensor which continuously captures the rotation signal. Using a joint interrogation scheme, where we simultaneously prepare a cold-atom source and ...operate an atom interferometer (AI), enables us to eliminate the dead times. We show that such continuous operation improves the short-term sensitivity of AIs, and demonstrate a rotation sensitivity of 100 nrad/sec/sqrtHz in a cold-atom gyroscope of 11 cm^{2} Sagnac area. We also demonstrate a rotation stability of 1 nrad/sec at 10^{4} sec of integration time, which represents the state of the art for atomic gyroscopes. The continuous operation of cold-atom inertial sensors will lead to large area AIs at their full sensitivity potential, determined by the quantum noise limit.
There is a critical need for improved methane-oxidation catalysts to both reduce emissions of methane, a greenhouse gas, and improve the performance of gas turbines. However, materials that are ...currently available either have low activity below 400°C or are unstable at higher temperatures. Here, we describe a supramolecular approach in which single units composed of a palladium (Pd) core and a ceria (CeO(2)) shell are preorganized in solution and then homogeneously deposited onto a modified hydrophobic alumina. Electron microscopy and other structural methods revealed that the Pd cores remained isolated even after heating the catalyst to 850°C. Enhanced metal-support interactions led to exceptionally high methane oxidation, with complete conversion below 400°C and outstanding thermal stability under demanding conditions.
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This work shows an easy and eco-friendly methodology to obtain almost pristine anatase phase of TiO2 by using furfural, a biomass-derived molecule, as a bio-template. The ...photocatalytic activity was studied following the degradation of methylene blue and phenol under artificial solar irradiation. Results were compared against those obtained on a commercial pristine anatase TiO2. The pseudo first-order, the second-order and the intraparticle diffusion kinetic models were verified. The textural and surface chemistry properties of the materials were correlated with the surface density of molecules adsorbed in equilibrium. The reaction-rate showed an almost perfect quadratic regression as a function of the surface density. Theoretical estimations of the density of states by DFT + U were performed showing that the total electron charge in the oxygen bonded to anatase TiO2 increased due to carbon doping in agreement with the prediction of appearance of atomic orbitals 2p from carbon atom in the hybrid material. C-doping is responsible of the red-shift from 3.14 to 2.94 eV observed for a Ti15O32C super-cell than pristine anatase Ti16O32. The increase in the activity of the C-doped TiO2 photocatalyst was due to the decrease in the energy band-gap promoting a higher absorption of photons from the visible light.
A novel, homogeneous, nanostructured and equiatomic (TiZrHfVNb)C5 High Entropy Carbide (HEC) was successfully synthesised in a powder form by a mechanosynthesis process from the elemental mixture. ...This synthesis method for HECs, not previously reported, is simple, reproducible and carried out at room temperature. During milling, the transition metals (Ti, Zr, Hf, V and Nb) alloying and the diffusion of carbon (introduced as graphite) into the alloy structure are simultaneously induced, obtaining the expected (TiZrHfVNb)C5 HEC. The room temperature method employed contrasts with those reported in the bibliography from binary carbides that are carried out at a very high temperature (1800–2200 °C), with the consequent energy savings.
► We grow Scenedesmus obliquus in urban wastewater in batch and continuous operation. ► Biomass in continuous operation can be predicted based on batch growth kinetics. ► Optimum operation residence ...times are based on specific growth rate from batch. ► Optimum hydraulic retention time depends on the objective of the culture.
A laboratory-scale flat panel photobioreactor was operated for the continuous growth of Scenedesmus obliquus and consequent removal of nutrients in wastewater. This study develops a simple model by which biomass values in continuous operation can be predicted from kinetic growth parameters obtained from a shorter batch experiment. Based on this study, biomass concentrations and productivities in continuous operation can be successfully predicted as a function of the specific hydraulic retention time (HRT) assumed. Considerable biomass production and nutrient uptake from wastewater were achieved in the experiment. Optimum operating conditions for the reactor depend on the particular objective: the maximization of biomass production and carbon dioxide biofixation involves a HRT of 2μ−1 (specific growth rate), whereas efficient nutrient removal involves a HRT as close as possible to μ−1 (as long as discharges comply fully with the parameters set); alternatively biomass intended for biodiesel or biogas production would involve a HRT>2μ−1.
A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints, this field requires advancements in three ...principle directions: (a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and microlevels of organization; (b) understanding disassembly/deconstruction processes; and (c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: (1) nucleation of early PbS NPs with an average diameter of 31 nm; (2) assembly into 100–500 nm octahedral mesocrystals; (3) assembly into 1000–2500 nm hyperbranched stars; (4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; (5) deconstruction into rods and cuboctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern-determining forces that include van der Waals and electrostatic (charge–charge, dipole–dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy-harvesting devices which require organization of PbS components at multiple scales.
Small heat shock proteins are a rather heterogeneous family of ATP-independent chaperones, some of which have been proven to block protein aggregation and help the cells to survive stressful ...conditions. Although much less studied than high molecular weight HSPs like HSP70/HSPA or HSP90/HSPC, their implication in physio-pathological processes and human diseases is now well evidenced, as it will be discussed in the different reviews of this special issue. In this mini-review we will just present a general introduction about the small heat shock proteins family.
This article is part of a Directed Issue entitled: Small HSPs in physiology and pathology.
In healthy cells, cytochrome c (Cyt c) is located in the mitochondrial intermembrane/intercristae spaces, where it functions as an electron shuttle in the respiratory chain and interacts with ...cardiolipin (CL). Several proapoptotic stimuli induce the permeabilization of the outer membrane, facilitate the communication between intermembrane and intercristae spaces and promote the mobilization of Cyt c from CL, allowing for Cyt c release. In the cytosol, Cyt c mediates the allosteric activation of apoptosis-protease activating factor 1, which is required for the proteolytic maturation of caspase-9 and caspase-3. Activated caspases ultimately lead to apoptotic cell dismantling. Nevertheless, cytosolic Cyt c has been associated also to vital cell functions (i.e. differentiation), suggesting that its release not always occurs in an all-or-nothing fashion and that mitochondrial outer membrane permeabilization may not invariably lead to cell death. This review deals with the events involved in Cyt c release from mitochondria, with special attention to its regulation and final consequences.
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