Preparation of planar‐chiral multidonor phosphanylferrocene carboxamides and their application as ligands for palladium‐catalysed asymmetric allylic alkylation

Amide coupling of (S_p)‐2‐(diphenylphosphanyl)ferrocene‐1‐carboxylic acid with appropriate terminal amines mediated by 1‐hydroxybenzotriazole and a carbodiimide affords multi‐donor amides terminally functionalized with planar‐chiral (S_p)‐2‐(diphenylphosphanyl)ferrocen‐1‐yl moieties in good to excellent yields. Palladium catalysts based on these ligands efficiently promote asymmetric allylic alkylation of 1,3‐diphenylallyl acetate with in situ generated dimethyl malonate anion to give the C‐alkylated product with ees up to 93% at room temperature. Copyright © 2010 John Wiley & Sons, Ltd.     

A blue luminescent binuclear cadmium-orotate coordination polymer: synthesis,crystal structure,and thermogravimetric analysis

Assembly of orotic acid (H₃Or, 1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic) and Cd(NO₃)·6H₂O yielded a coordination polymer, [(Cd(Hor)·2.5H₂O)₂]_n (1), which has been characterized by X-ray single-crystal diffraction, TGA, and ?uorescence spectra. Single-crystal X-ray structural analyses reveal that 1 is a hydrogen-bonded binuclear Cd-orotate coordination polymer in which both Cd²⁺ ions have different coordination environments with identical distorted octahedral geometry. Crystal data for 1: monoclinic, space group P2₁/n, a = 7.0209(10) Å, b = 13.974(2) Å, c = 17.541(3) Å, β = 98.842(2)°, V = 1700.5(4) Å, Z = 4, R1 = 0.0269, wR2 = 0.0612, θ_max = 25.960. The emission spectrum of the Cd-complex recorded with 265 nm excitation wavelength reveals the complex has strong blue luminescence with the peak maximum 420 nm (2.95 eV) as a result of the n–π* and π–π* transitions on the H₃Or ligand.     

Inventory control with an order-time constraint: optimality,uniqueness and significance

This paper analyzes a stochastic inventory problem with an order-time constraint that restricts the times at which a manufacturer places new orders to a supplier. This constraint stems from the limited upstream capacity in a supply chain, such as production capacity at a supplier or transportation capacity between a supplier and a manufacturer. Consideration of limited upstream capacity extends the classical inventory literature that unrealistically assumes infinite supplier/transporter capacity. But this consideration increases the complexity of the problem. We study the constraint under a Poisson demand process and allow for a fixed ordering cost. In presence of the constraint, we establish the optimality of an (s,S) policy under both the discounted and average cost objectives. Under the average cost objective, we show the uniqueness of the order-up-to level S. We numerically compare our model with the classical unconstrained model. We report significant savings in costs that can be achieved by using our model when the order time is constrained.     

Reserve stock models: Deterioration and preventive replenishment

Reserve stocks are needed in a wide spectrum of industries from strategic oil reserves to tactical (machine buffer) reserves in manufacturing. One important aspect under-looked in research is the effect of deterioration, where a reserve stock, held for a long time, may be depleted gradually due to factors such as spoilage, evaporation, and leakage. We consider the common framework of a reserve stock that is utilized only when a supply interruption occurs. Supply outage occurs randomly and infrequently, and its duration is random. During the down time the reserve is depleted by demand, diverted from its main supply. We develop optimal stocking policies, for a reserve stock which deteriorates exponentially. These policies balance typical economic costs of ordering, holding, and shortage, as well as additional costs of deterioration and preventive measures. Our main results are showing that (i) deterioration significantly increases cost (up to 5%) and (ii) a preventive replenishment policy, with periodic restocking, can offset some of these additional costs. One side contribution is refining a classical reserve stock model (Hansmann, 1962).     

2D hydrogen-bonded manganese–picolinate coordination network: ionic liquid-induced synthesis,crystal structure and thermogravimetric analysis

A new manganese coordination complex of formula [Mn(2-picolinate)₂·2H₂O]·H₂O based on 2-picolinic acid has been synthesized hydrothermally at 120 °C for 48 h in presence of ionic liquid tetraethylammonium hydroxide (25% methanolic solution). 1 crystallizes in monoclinic crystal system and is hydrogen-bonded metal-organic network in which aqua ligands are instrumental in deciding structural features. The reported complex 1 is insoluble in almost all organic solvents as well as in water and shows good thermal stability upto 450 °C.     

Giant Hysteretic Sorption of CO2: In Situ Crystallographic Visualization of Guest Binding within a Breathing Framework at 298 K

A dynamic Zn^II‐MOF has been shown to exhibit extreme breathing behavior under gas pressure. The very narrow pore form of the activated framework opens up in the presence of carbon dioxide, thus making it a suitable material for CO₂ capture. Sorption of CO₂ at 298 K and relatively high pressure clearly shows a two‐step isotherm with giant hysteresis for the second step. In‐situ single‐crystal diffraction analysis was carried out under CO₂ gas pressure at 298 K using an environmental gas cell in order to visualize the interaction between CO₂ and the host framework. The results are well supported by pressure‐gradient differential scanning calorimetry (P‐DSC) and variable‐pressure powder X‐ray analysis. Theoretical calculations have been carried out in order to further back up the crystallographic data.     

Spectrofluorimetric Determination of Fluvoxamine in Dosage Forms and Plasma Via Derivatization with 4-Chloro-7-Nitrobenzo-2-Oxa-1,3-Diazole

A highly sensitive and simple spectrofluorimetric method has been developed and validated for the determination of the antidepressant fluvoxamine (FXM) in its dosage forms and plasma. The method was based on nucleophilic substitution reaction of FXM with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole in an alkaline medium (pH 8) to form a highly fluorescent derivative that was measured at 535 nm after excitation at 470 nm. The factors affecting the reaction was carefully studied and optimized. The kinetics of the reaction was investigated, and the reaction mechanism was presented. Under the optimized conditions, linear relationship with good correlation coefficient (0.9995) was found between the fluorescence intensity and FXM concentration in the range of 65–800 ng ml⁻¹. The limits of detection and quantitation for the method were 21 and 64 ng ml⁻¹, respectively. The precision of the method was satisfactory; the values of relative standard deviations did not exceed 2.17%. The proposed method was successfully applied to the determination of FXM in its pharmaceutical tablets with good accuracy; the recovery values were 97.8–101.4 ± 1.08–2.75%. The results obtained by the proposed method were comparable with those obtained by the official method. The high sensitivity of the method allowed its successful application to the analysis of FXM in spiked human plasma. The proposed method is superior to the previously reported spectrofluorimetric method for determination of FXM in terms of its simplicity. The proposed method is practical and valuable for its routine application in quality control and clinical laboratories for analysis of FXM.