A Mechanistic Dichotomy in Two-Electron Reduction of Dioxygen Catalyzed by N,N’-Dimethylated Porphyrin Isomers

Selective two-electron reduction of dioxygen (O₂) to hydrogen peroxide (H₂O₂) has been achieved by two saddle-distorted N,N’-dimethylated porphyrin isomers, an N21,N’22-dimethylated porphyrin ( anti -Me₂P ) and an N21,N’23-dimethylated porphyrin ( syn -Me₂P ) as catalysts and ferrocene derivatives as electron donors in the presence of protic acids in acetonitrile. The higher catalytic performance in an oxygen reduction reaction (ORR) was achieved by anti -Me₂P with higher turnover number (TON=250 for 30 min) than that by syn -Me₂P (TON=218 for 60 min). The reactive intermediates in the catalytic ORR were confirmed to be the corresponding isophlorins ( anti -Me₂Iph or syn -Me₂Iph ) by spectroscopic measurements. The rate-determining step in the catalytic ORRs was concluded to be proton-coupled electron-transfer reduction of O₂ with isophlorins based on kinetic analysis. The ORR rate by anti -Me₂Iph was accelerated by external protons, judging from the dependence of the observed initial rates on acid concentrations. In contrast, no acceleration of the ORR rate with syn -Me₂Iph by external protons was observed. The different mechanisms in the O₂ reduction by the two isomers should be derived from that of the arrangement of hydrogen bonding of a O₂ with inner NH protons of the isophlorins.     

Single Machine Batch Scheduling Problem with Resource Dependent Setup and Processing Time in the Presence of Fuzzy Due Date

We consider a batch scheduling problem on a single machine which processes jobs with resource dependent setup and processing time in the presence of fuzzy due-dates given as follows:1. There are n independent non-preemptive and simultaneously available jobs processed on a single machine in batches. Each job j has a processing time and a due-date.2. All jobs in a batch are completed together upon the completion of the last job in the batch. The batch processing time is equal to the sum of the processing times of its jobs. A common machine setup time is required before the processing of each batch.3. Both the job processing times and the setup time can be compressed through allocation of a continuously divisible resource. Each job uses the same amount of the resource. Each setup also uses the same amount of the resource.4. The due-date of each job is flexible. That is, a membership function describing non-decreasing satisfaction degree about completion time of each job is defined.5. Under above setting, we find an optimal batch sequence and resource values such that the total weighted resource consumption is minimized subject to meeting the job due-dates, and minimal satisfaction degree about each due-date of each job is maximized. But usually we cannot optimize two objectives at a time. So we seek non-dominated pairs i.e. the batch sequence and resource value, after defining dominance between solutions.A polynomial algorithm is constructed based on linear programming formulations of the corresponding problems.     

A Crop Planning Problem with Fuzzy Random Profit Coefficients

The main purpose of this paper is to present a crop planning problem for agricultural management under uncertainty. It is significant that agricultural managers assign their limited farmlands to cultivation of which crops in a season. This planning is called the crop planning problem and influences their incomes for the season. Usually, the crop planning problem is formulated as a linear programming problem. But there are many uncertain factors in agricultural problems, so future profits for crops are not certain values. A linear programming model with constant profit coefficients may not reflect the environment of decision making properly. Therefore, we propose a model of crop planning with fuzzy profit coefficients, and an effective solution procedure for the model. Furthermore, we extend this fuzzy model, setting the profit coefficients as discrete randomized fuzzy numbers. We show concrete optimal solutions for each models.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Space- and time-like electromagnetic pion form factors in light-cone pQCD

We present a combined analysis of the space- and time-like electromagnetic pion form factors in light-cone perturbative QCD with transverse momentum dependence and Sudakov suppression. Including the genuine non-perturbative “soft” QCD and the power suppressed twist-3 corrections to the standard twist-2 perturbative QCD result, the experimental form factor data available at moderate energies/momentum transfers can be explained reasonably well. To this end, the bulk of the existing discrepancy between the space- and time-like experimental data is ostensibly reconciled.     

Circular autocorrelation of stationary circular Markov processes

The stationary Markov process is considered and its circular autocorrelation function is investigated. More specifically, the transition density of the stationary Markov circular process is defined by two circular distributions, and we elucidate the structure of the circular autocorrelation when one of these distributions is uniform and the other is arbitrary. The asymptotic properties of the natural estimator of the circular autocorrelation function are derived. Furthermore, we consider the bivariate process of trigonometric functions and provide the explicit form of its spectral density matrix. The validity of the model was assessed by applying it to a series of wind direction data.     

Analysis of membrane transport mechanisms of endogenous substrates using chromatographic techniques

Membrane transporters are expressed in various bodily tissues and play essential roles in the homeostasis of endogenous substances and the absortion, distribution and/or excretion of xenobiotics. For transporter assays, radioisotope‐labeled compounds have been mainly used. However, commercially available radioisotope‐labeled compounds are limited in number and relatively expensive. Chromatographic analyses such as high‐performance liquid chromatography with ultraviolet absorptiometry and liquid chromatography with tandem mass spectrometry have also been applied for transport assays. To elucidate the transport properties of endogenous substrates, although there is no difficulty in performing assays using radioisotope‐labeled probes, the endogenous background and the metabolism of the compound after its translocation across cell membranes must be considered when the intact compound is assayed. In this review, the current state of knowledge about the transport of endogenous substrates via membrane transporters as determined by chromatographic techniques is summarized. Chromatographic techniques have contributed to our understanding of the transport of endogenous substances including amino acids, catecholamines, bile acids, prostanoids and uremic toxins via membrane transporters.