Molecular Basis of the Chemiluminescence Mechanism of Luminol

Light emission from luminol is probably one of the most popular chemiluminescence reactions due to its use in forensic science, and has recently displayed promising applications for the treatment of cancer in deep tissues. The mechanism is, however, very complex and distinct possibilities have been proposed. By efficiently combining DFT and CASPT2 methodologies, the chemiluminescence mechanism has been studied in three steps: 1) luminol oxygenation to generate the chemiluminophore, 2) a chemiexcitation step, and 3) generation of the light emitter. The findings demonstrate that the luminol double-deprotonated dianion activates molecular oxygen, diazaquinone is not formed, and the chemiluminophore is formed through the concerted addition of oxygen and concerted elimination of nitrogen. The peroxide bond, in comparison to other isoelectronic chemical functionalities (−NH−NH−, −N⁻−N⁻−, and −S−S−), is found to have the best chemiexcitation efficiency, which allows the oxygenation requirement to be rationalized and establishes general design principles for the chemiluminescence efficiency. Electron transfer from the aniline ring to the OO bond promotes the excitation process to create an excited state that is not the chemiluminescent species. To produce the light emitter, proton transfer between the amino and carbonyl groups must occur; this requires highly localized vibrational energy during chemiexcitation.     

Locating and capacity planning for retailers of a new supply chain to compete on the plane

This paper investigates the network design problem of a two-level supply chain (SC), which is applicable for industries such as automotive, fuel and tyre manufacturing. Models presented in this paper aim at locating retail facilities of an SC and identifying their required capacities in the presence of existing competing retailers of a rival SC. We consider feasible locating space of the retail facilities on the continuous plane with bounded constraints and static competition among the rivals of the markets with deterministic demands. The problem is used for both essential and luxury product cases; hence, we consider elastic and inelastic demands, both. The models discussed in this paper are non-linear and non-convex which are difficult to solve. We use interval branch-and-bound as optimization algorithm for small size single-retailer problems, but for large-scale, multi-retailer problems we need to have more efficient methods. Therefore, we apply a heuristic algorithm (H1), a simulated annealing (SA) algorithm, an interior point (IP) algorithm, a genetic algorithm (GA) and a pattern search algorithm for solving multi-retailer problem with elastic and inelastic demands. Computational results obtained from performing different solution approaches for both elastic and inelastic show that mostly IP, PS, and H1 methods outperform the other approaches. The computational results on a real-life case are also promising. Several extended mathematical models and an example of a typical case with details are presented in the appendices of the paper.     

Liquid‐phase microextraction by solidification of floating organic microdrop and GC‐MS detection of trihalomethanes in drinking water

A simple and sensitive methodology based on liquid‐phase microextraction (LPME) followed by GC‐MS, was developed for the determination of trihalomethanes (THMs) in drinking water. A microdrop of organic solvent was floated on the surface of the aqueous sample and it was agitated for a desired time. Then, the sample vial was cooled by inserting it into an ice bath for 4 min. The solidified solvent was transferred into a suitable vial and immediately melted. The extract was directly injected into the GC. Microextraction efficiency factors were investigated and optimized: 7 μL 1‐undecanol microdrop exposed for 15 min floated on the surface of a 10.0 mL aqueous sample with the temperature of 60°C containing 3 M of NaCl and stirred at 750 rpm. Under the selected conditions, enrichment factors (EFs) up to 482‐fold, LOD of 0.03–0.08 μg/L (S/N = 3) and dynamic linear ranges of 0.10–100 μg/L were obtained. A reasonable repeatability (RSD < 8.6%, n = 8) with satisfactory linearity (r² ? 0.9947) of results illustrated a good performance of the present method. The protocol proved to be rapid, cost‐effective, and is a green procedure for the screening purposes.     

Modeling and analysis for determining optimal suppliers under stochastic lead times

The policy of simultaneously splitting replenishment orders among several suppliers has received considerable attention in the last few years and continues to attract the attention of researchers. In this paper, we develop a mathematical model which considers multiple-supplier single-item inventory systems. The item acquisition lead times of suppliers are random variables. Backorder is allowed and shortage cost is charged based on not only per unit in shortage but also per time unit. Continuous review (s,Q)$(s\text{,}Q)$ policy has been assumed. When the inventory level depletes to a reorder level, the total order is split among n suppliers. Since the suppliers have different characteristics, the quantity ordered to different suppliers may be different. The problem is to determine the reorder level and quantity ordered to each supplier so that the expected total cost per time unit, including ordering cost, procurement cost, inventory holding cost, and shortage cost, is minimized. We also conduct extensive numerical experiments to show the advantages of our model compared with the models in the literature. According to our extensive experiments, the model developed in this paper is the best model in the literature which considers order splitting for n-supplier inventory systems since it is the nearest model to the real inventory system.     

The AdS4 Gravitational Perturbation and?Supersymmetry

Gravitational perturbation in AdS ₄, decomposed into axial and polar perturbations that have different parities. After imposing geometric perturbation in to the spherical, symmetric and static metric of AdS ₄, we can calculate the possible spectrum of frequencies around the static configuration. This spectrum relates to the boundary conditions imposed at spatial infinity (r=∞) and will be implied by the wave function’s behavior at x=\fracp2x=\frac{\pi}{2} or y=1. At the end we write down the first order raising and lowering operators from the second order Schr?dinger equation to study the supersymmetry model and check whether we have supersymmetric partners or no. After finding the H ₁ and the partner H ₂, we check the supersymmetry. At the end, we find the potentials to confirm the shape invariance condition and also the supercharges and their commutative relations are studied.     

Investigation of kinetic and mechanism of triphenylphosphine addition to para‐naphthoquinone

This work reports the results of a kinetic and mechanistic investigations of the addition reaction of triphenylphosphine to para‐naphtoquinone in 1,2‐dichloromethane as solvent. The order of reaction with respect to the reactants was determined using initial rate method, and the rate constant was obtained on the basis of pseudo‐first‐order method. Variable time method using Uv–Vis spectrophotometry (at 400 nm) was utilized for monitoring this addition reaction, for which the following Arrhenius equation was obtained: The resulting activation parameters E_a, ΔH^#, ΔG^#, and ΔS^# at 300 K were 13.63, 14.42, 18.75 kcal mol^?1, and ?14.54 cal mol^?1K^?1, respectively. The results suggest that the reaction is first order with respect to both triphenylphosphine and para‐naphthoquinone. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 427–433, 2005     

Single quantum dot coupled to a scanning optical antenna: a tunable superemitter

The interaction of a single quantum dot with a bowtie antenna is demonstrated for visible light. The antenna is generated at the apex of a Si3N4 atomic force microscopy tip by focused ion beam milling. When scanned over the quantum dot, its photoluminescence is enhanced while its excited-state lifetime is decreased. Our observations demonstrate that the relaxation channels of a single quantum emitter can be controlled by coupling to an efficiently radiating metallic nanoantenna.     

Kinetic modeling of the ethylbenzene/xylene isomerization reaction over HZSM-5 zeolites revisited

In this article, a binderless dealuminated HZSM-5 zeolite (Si/Al = 41.4) was used as a catalyst for the isomerization of a mixture of ethylbenzene and xylene. The experimental results indicated that at low residence times the catalyst is effective to isomerize the ethylbenzene into xylenes. A comprehensive kinetic model considering chemisorption, surface chemical reactions, and diffusional processes was developed for this reaction. The intrinsic activation energy (71.99 kJ mol⁻¹) for the surface reaction of ethylbenzene into m-xylene was calculated for the first time, and the corresponding intrinsic activation energies for o-xylene to m-xylene and m-xylene to p-xylene surface reactions were calculated to be 59.45 and 50.68 kJ mol⁻¹, respectively. Lower apparent values have been reported in the literature, and we rationalize that they correspond to multistep processes and intrinsically include a negative activation energy pertaining to chemisorption. The results also revealed that the ethylbenzene diffusion within the zeolite channels was four orders of magnitude smaller than p-xylene.     

Thermodynamical Stability of Hagedorn and Radiation Regimes in Closed String Gas Cosmology

In this paper, we investigate thermal equilibrium in string gas cosmology which is dominated by closed string. We consider two interesting regimes, Hagedorn and radiation regimes. We find that for short strings in small radius of Hagedorn regime very large amount of energy requested to have thermal equilibrium but for long strings in such system a few energy is sufficient to have thermal equilibrium. On the other hand in the large radius of Hagedorn regime, which pressure is not negligible, we obtain a relation between the energy and pressure in terms of cosmic time which is satisfied by thermal equilibrium. Then we discuss about radiation regime and find that in all cases there is thermal equilibrium.