T1–T2 Correlation Spectra Obtained Using a Fast Two-Dimensional Laplace Inversion

Spin relaxation is a sensitive probe of molecular structure and dynamics. Correlation of relaxation time constants, such as T₁ and T₂, conceptually similar to the conventional multidimensional spectroscopy, have been difficult to determine primarily due to the absense of an efficient multidimensional Laplace inversion program. We demonstrate the use of a novel computer algorithm for fast two-dimensional inverse Laplace transformation to obtain T₁–T₂ correlation functions. The algorithm efficiently performs a least-squares fit on two-dimensional data with a nonnegativity constraint. We use a regularization method to find a balance between the residual fitting errors and the known noise amplitude, thus producing a result that is found to be stable in the presence of noise. This algorithm can be extended to include functional forms other than exponential kernels. We demonstrate the performance of the algorithm at different signal-to-noise ratios and with different T₁–T₂ spectral characteristics using several brine-saturated rock samples.     

Diffusion-relaxation distribution functions of sedimentary rocks in different saturation states

We present diffusion-relaxation distribution functions measured on four rock cores that were prepared in a succession of different saturation states of brine and crude oil. The measurements were performed in a static gradient field at a Larmor frequency of 1.76 MHz. The diffusion-relaxation distribution functions clearly separate the contributions from the two fluid phases. The results can be used to identify the wetting and non-wetting phase, to infer fluid properties of the phases, and to obtain additional information on the geometrical arrangement of the phases. We also observe effects due to restricted diffusion and susceptibility induced internal gradients.     

Radical dearomatization of benzene leading to phenanthridine and phenanthridinone derivatives related to (±)-pancratistatin

The synthesis of the phenanthridinone nucleus common to the Amaryllidaceae series of natural products is achieved by a sequence involving tributylstannane-mediated, benzeneselenol-catalyzed addition of ortho-nitrogen functionalized aryl radicals to benzene, yielding aryl-substituted cyclohexadienes. These cyclohexadienes may be manipulated by oxidative ring closure sequences to generate functionalized phenanthridines. Beginning from 2-hydroxy-6-iodopiperonic acid a key intermediate in the Danishefsky synthesis of (±)-pancratistatin is achieved in two steps.     

Rejuvenating the Geometric Electrocatalytic OER Performance of Crystalline Co3O4 by Microstructure Engineering with Sulfate

Despite significant research on its electrocatalytic OER activity, the geometric performance of Co₃O₄ has remained unsatisfactory compared to relatively amorphous Co-based materials. In particular, the activity of Co₃O₄ prepared through annealing always gets inferior compared to its amorphous precursor. This demands the development of synthetic techniques to prepare Co₃O₄ with superior activity as the unpredictable crystal structure of the amorphous materials makes it difficult to understand their structure-activity relationships despite higher geometric activity. In this article, we have shown that incorporation of sulfate in pre-annealed materials plays a pivotal role in boosting the OER activity of annealed Co₃O₄ irrespective of the pre-annealed phase. In contrast to commonly used nitrate or carbonate that leaves the structure upon annealing and renders the resulting Co₃O₄ with poor activity, sulfate remains in the annealed structure due to its thermal stability and causes a dramatic enhancement in the geometric electrocatalytic OER activity of resulting Co₃O₄ compared to the pre-annealed phase. This was due to the “pore-alteration ability” and “crystallization hindrance effect” of sulfate ions that significantly alter the microstructure of the resulting Co₃O₄ during annealing process by dramatically improving the surface area, pore size, and pore volume. Moreover, sulfate incorporation provided structures with considerably higher mesoporosity that is known to be conducive for reactant and product diffusion within the network. The improved textural properties led to better exposure of the catalytic centres to the electrolyte leading to higher geometric OER activity despite identical intrinsic activity of both sulfate free and incorporated Co₃O₄ as confirmed from their specific activities. Further, the Co₃O₄ synthesized by annealing sulfate incorporated precursor was found to be rich with oxygen defects that are known to increase the potency of a material towards electrocatalytic OER. The sulfate ions also etched out in the electrolyte during electrocatalysis leading to complete unblocking of the pores thereby helping in sustaining the high geometric OER activity. To our knowledge, this is the first report where the geometric electrocatalytic OER activity of an annealed Co₃O₄ is significantly better compared to its pre-annealed phase and is in fact comparable to the activity of amorphous Co-hydroxide based compounds.     

Service and cost benefits through clicks-and-mortar integration: Implications for the centralization/decentralization debate

Traditional “Brick-and-Mortar” operations face the challenge of adapting to a new set of competitive rules made necessary by consumers who want the option of ordering electronically via the Internet. To satisfy these customers, firms must develop strategies that integrate their standard retail in-store channel with this relatively new on-line channel. Therefore, this research is designed to provide insights into supply chain inventory management strategies relevant to “Clicks-and-Mortar” firms trying to satisfy both on-line and in-store sales. Specifically, this work considers the total cost implications of various inventory allocation strategies while maintaining target customer service levels. Analysis focuses on the development of models capable of handling new operating strategies made possible by electronic commerce. The implications of inventory risk pooling are considered in depth, revealing the existence of characteristics that determine whether completely centralized or decentralized policies are preferable.     

An algorithm for solving the multi-period online fulfillment assignment problem

This paper develops an optimal solution procedure for the multi-period online fulfillment assignment problem to determine how many and which of a retailer/e-tailer’s capacitated regional warehouse locations should be set up to handle online sales over a finite planning horizon. To reduce the number of candidate solutions in each period, dominance rules from the facility location literature are extended to handle the nonlinear holding and backorder cost implications of our problem. Computational results indicate that multi-period considerations can play a major role in determining the optimal set of online fulfillment locations. In 92% of our test problems, the multi-period solution incorporated fewer openings and closings than myopic single period solutions. To illustrate the use of the model under changing demands, the multi-period solution yielded different supply chain configurations than the myopic single period solution in over 37% of the periods.     

Electronic structures and spectra of symmetric meso‐substituted porphyrin: DFT and TDDFT—PCM investigations

DFT and TDDFT calculations at the level of PBE0/6‐31G(d)/6‐31+G(d) were performed systematically on seven porphyrins with symmetrical meso‐substitutents. Our results show that the planarity of the free base porphyrin (BP) are affected by the introduction of substitutents at the meso‐position of the ring. Geometrical studies show that the introduction of electron‐withdrawing groups brings about in‐plane deformation in the porphyrin ring, whereas the bulky substitutents make an out‐of‐plane deformation. However, FMO's diagram shows that electron‐withdrawing groups alter the degeneracy of the HOMO and HOMO ?1 orbtial. Up on introduction of substituents at the meso‐position, the Q band FMOs transitions were the same as in the case of free BP; however, the oscillator strength is changed. Electron releasing substituted at the meso‐position shows bathochromic shift in the Q band region. However, the intensity or the hyperchromic shift is higher for the electron withdrawing groups. Solvation studies show that Q bands are blue shifted and B bands are red shifted, whereas the intensity of the B bands was highly enhanced compared with the Q bands. These theoretical studies would be helpful in designing new porphyrins for the photodynamic therapy and dye‐sensitized solar cell applications. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011