Transport in ceria electrolytes modified with sintering aids: effects on oxygen reduction kinetics

Small (2 mol%) cobalt oxide additions to ceria-gadolinia (CGO) materials considerably improve sinterability, making it possible to obtain ceramics with 95–99% density and sub-micrometre grain sizes at 1,170–1,370 K. The addition of Co causes a significant shift of the electrolytic domain to lower pO₂. This modification to the minor electronic conductivity of the electrolyte material has influence on the cathodic oxygen reduction reaction. The impedance technique is shown to provide information not only about polarisation resistance, but also about the active electrode area from analysis of the current constriction resistance. It is demonstrated that this current constriction resistance can be related to the minor electronic contributions to total conductivity in these materials. A simple imbedded grid approach gives control of the contact area allowing the properties of the electrolyte materials to be studied. A much lower polarisation resistance for the Co-containing CGO electrolyte is observed, which can be clearly attributed to an increased three-phase reaction area in the Co-containing material, as a consequence of elevated p-type conductivity.     

Solar-Driven Artificial Carbon Cycle

Constituting the artificial carbon cycle,for example,through recycling CO₂ and converting CH₄ to value-added fuels and chemicals with solar energy,offers a sustainable future for humankind to tackle the global environmental issues and energy crisis.However,significant bottlenecks remain in such photocatalytic conversion,mainly related to the reaction activity and product selectivity.Herein,we share our efforts and systematic research progress on addressing the double bottlenecks for achieving solar-driven artificial carbon cycle,with specifically focusing on the photocatalytic CO₂ and CH₄ conversion.We further elucidate the common fundamentals behind various designed photocatalytic materials systems.Toward future development,we highlight the opportunities and challenges in the research field.     

Improved synthesis of a [4.4]-spirolactam β-turn mimetic as surrogate of the didemnin side chain dipeptide Pro-N-Me-d-Leu

An efficient synthesis of [4.4]-spirolactam restricted derivatives of the didemnin side chain dipeptide l-Pro-N-Me-d-Leu is described. This methodology involves: (a) peptide coupling of N-Boc-2-allylproline with d-Leu-OBn; (b) OsO₄/NaIO₄ mediated allyl oxidation and intramolecular cyclization to the corresponding cyclic hemiaminals; and (c) NaBH₄ mediated reduction of an intermediate N-acyliminium ion. This synthetic strategy gave significant better results than the previously reported strategies for the synthesis of [4.4]-spirolactam β-turn mimetics.     

Oxidation-Reduction Conversions of Derivatives of 1,4-Dihydropyridine and 4H-pyran on Interaction of Alicyclic 1,5-Diketones wth 4-Aminoazobenzene

The interaction of 2,2'-methylenedicyclohexanone and 2,2'-methylenedicyclopentanone with 4-aminoazobenzene in acetic acid leads to reduction of the azo group of 1,4-dihydropyridine and 4H-pyran derivatives formed as intermediates. The reduction products were isolated as the corresponding pyridinium salts.     

The effect of composition of parenteral solution on the thermal resistance of Bacillus stearothermophilus and Bacillus subtilis spores

Large-volume parenteral solutions were submitted to heat treatments after being inoculated with Bacillus stearothermophilus ATCC 7953 (T _r =121°C) and Bacillus subtilis ATCC 9372 (T _r =104.5°C) spores. The average decimal reduction time for B. stearothermophilus ranged from a D _121°C value of 1.31 to 3.14 min, in glucophysiologic and Ringer’s solutions respectively. For B. subtilis, D _104.5°C value increased from 0.69 to 1.37 min, in Ringer’s (pH=5.91) and 50% glucose (pH 3.05) solutions respectively. The z value ranged from 7.95°C (20% mannitol solution) to 13.14°C (50% glucose solution), corresponding to an activation energy (Ea) of 81.48 and 49.30 kcal/mol, respectively.     

费-托合成铁-钼/活性炭催化剂还原和碳化的穆斯堡尔谱研究

以原位穆斯堡尔谱研究了活性炭担载的费-托合成铁-钼双金属催化剂的还原和碳化行为。在H_2中不同温度下还原催化剂,其中的Fe~(3+)还原为Fe~(2+),进而还原为Fe~0。但在400—450℃间发生了还原铁物类的再氧化现象,可归因于磷钼酸根Keggin结构的热分解。在500℃H_2中,铁和钼都还原为金属并形成合金,其穆斯堡尔谱为一单峰,同质异能移为-0.16mm/s。再在300℃合成气(2H_2/CO)中碳化,可生成Fe-Mo碳化物(Fe_(1-y)Mo_y)_xC,穆斯堡尔谱为δ～0.17mm/s,△～0.64mm/s的双峰。     

Minimum energy configurations on a toric lattice as a quadratic assignment problem

We consider three known bounds for the quadratic assignment problem (QAP): an eigenvalue, a convex quadratic programming (CQP), and a semidefinite programming (SDP) bound. Since the last two bounds were not compared directly before, we prove that the SDP bound is stronger than the CQP bound. We then apply these to improve known bounds on a discrete energy minimization problem, reformulated as a QAP, which aims to minimize the potential energy between repulsive particles on a toric grid. Thus we are able to prove optimality for several configurations of particles and grid sizes, complementing earlier results by Bouman et al. (2013). The semidefinite programs in question are too large to solve without pre-processing, and we use a symmetry reduction method by Permenter and Parrilo (2020) to make computation of the SDP bounds possible.     

Complex homogeneous spaces of real groups with top homology in codimension two

SupposeX=G/H is a connected homogeneous complex manifold, whereG is a Lie group andH is a closed subgroup. Assume (X) and letG/H G/I be the holomorphic reduction ofX. If the top nonvanishing homology group ofX with coefficients in ₂ is in codimension two, then either a complex Lie group acts tansitively onG/I (see [3]) orG/I is biholomorphic to the unit disk.Partially supported by NSERC Grant A3494 and by the Deutsche Forschungsgemeinschaft     

Potential reduction method for harmonically convex programming

In this paper, we introduce a potential reduction method for harmonically convex programming. We show that, if the objective function and them constraint functions are allk-harmonically convex in the feasible set, then the number of iterations needed to find an -optimal solution is bounded by a polynomial inm, k, and log(1/). The method requires either the optimal objective value of the problem or an upper bound of the harmonic constantk as a working parameter. Moreover, we discuss the relation between the harmonic convexity condition used in this paper and some other convexity and smoothness conditions used in the literature.The authors like to thank Dr. Hans Nieuwenhuis for carefully reading this paper and the anonymous referees for the worthy suggestions.     

Electrochemical synthesis of 1,2,3,4,4,5,6-substituted 1,4-dihydropyridines

It has been shown that chemical oxidation of the methyl ester of 3,4,5-trimethoxycarbonyl-1,2,6-trimethyl-1,4-dihydropyridine to the pyridinium salt, requiring forcing experimental conditions, may be replaced by electrochemical oxidation. On electrochemical reduction of 3,4,5-trimethoxycarbonyl-1,2,6-trimethylpyridinium perchlorate in the presence of alkylating agents 1,2,3,4,4,5,6-substituted 1,4-dihydropyridines are obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 226–237, February, 2007.