Two storage inventory model with fuzzy deterioration over a random planning horizon

An inventory model for a deteriorating item with stock dependent demand is developed under two storage facilities over a random planning horizon, which is assumed to follow exponential distribution with known parameter. For crisp deterioration rate, the expected profit is derived and maximized via genetic algorithm (GA). On the other hand, when deterioration rate is imprecise then optimistic/pessimistic equivalent of fuzzy objective function is obtained using possibility/necessity measure of fuzzy event. Fuzzy simulation process is proposed to maximize the optimistic/pessimistic return and finally fuzzy simulation-based GA is developed to solve the model. The models are illustrated with some numerical data. Sensitivity analyses on expected profit function with respect to distribution parameter λ and confidence levels α₁ and α₂ are also presented.     

Small-angle neutron scattering studies on water soluble complexes of poly(ethylene glycol)-based cationic random copolymer and SDS

The interaction of cationic random copolymers of methoxy poly(ethylene glycol) monomethacrylate and (3-(methacryloylamino)propyl) trimethylammonium chloride with oppositely charged surfactant, sodium dodecyl sulphate, and the influence of surfactant association on the polymer conformation have been investigated by small-angle neutron scattering. SANS data showed a positive indication of the formation of RCPSDS complexes. Even though the complete structure of the polyion complexes could not be ascertained, the results obtained give us the information on the local structure in these polymer-surfactant systems. The data were analysed using the log-normal distribution of the polydispersed spherical aggregate model for the local structure in these complexes. For all the systems the median radius and the polydispersity were found to be in the range of 20 ± 2 Å and 0.6 ± 0.05, respectively.     

Two-storage inventory model with lot-size dependent fuzzy lead-time under possibility constraints via genetic algorithm

Multi-item inventory models with stock dependent demand and two storage facilities are developed in a fuzzy environment where processing time of each unit is fuzzy and the processing time of a lot is correlated with its size. These are order-quantity reorder-point models with back-ordering if required. Here possibility and crisp constraints on investment and capacity of the small storehouse respectively are considered. The models are formulated as fuzzy chance constrained programming problem and is solved via generalized reduced gradient (GRG) technique when crisp equivalent of the constraints are available. A genetic algorithm (GA) is developed based on fuzzy simulation and entropy where region of search space gradually decreases to a small neighborhood of the optima and it is used to solve the models whenever the equivalent crisp form of the constraint is not available. The models are illustrated with some numerical examples and some sensitivity analyses have been done. For some particular cases results observed via GRG and GA are compared.     

Palladium(II)‐Catalyzed meta‐CH Olefination: Constructing Multisubstituted Arenes through Homo‐Diolefination and Sequential Hetero‐Diolefination

Divinylbenzene derivatives represent an important class of molecular building blocks in organic chemistry and materials science. Reported herein is the palladium‐catalyzed synthesis of divinylbenzenes by meta‐C? H olefination of sulfone‐based arenes. Successful sequential olefinations in a position‐selective manner provided a novel route for the synthesis of hetero‐dialkenylated products, which are difficult to access using conventional methods. Additionally, 1,3,5‐trialkenylated compounds can be generated upon successful removal of the directing group.     

Contrasting Response of Two Dipolar Fluorescence Probes in a Leucine‐Based Organogel and Its Implications

The microenvironments of a leucine‐based organogel are probed by monitoring the fluorescence behavior of coumarin 153 (C153) and 4‐aminophthalimide (AP). The steady‐state data reveals distinctly different locations of the two molecules in the gel. Whereas AP resides close to the hydroxyl moieties of the gelator and engages in hydrogen‐bonding interactions, C153 is found in bulk‐toluene‐like regions. In contrast to C153, AP exhibits excitation‐wavelength‐dependent emission, indicating that the environments of the hydrogen‐bonded AP molecules are not all identical. A two‐component fluorescence decay of AP in gel, unlike C153, supports this model. A time‐resolved fluorescence anisotropy study of the rotational motion of the molecules also reveals the strong association of only AP with the gelator. That AP influences the critical gelation concentration implies its direct involvement in the gel‐formation process. The results highlight the importance of guest–gelator interactions in gels containing guest molecules.     

Co-operative intra-protein structural response due to protein–protein complexation revealed through thermodynamic quantification: study of MDM2-p53 binding

The p53 protein activation protects the organism from propagation of cells with damaged DNA having oncogenic mutations. In normal cells, activity of p53 is controlled by interaction with MDM2. The well understood p53-MDM2 interaction facilitates design of ligands that could potentially disrupt or prevent the complexation owing to its emergence as an important objective for cancer therapy. However, thermodynamic quantification of the p53-peptide induced structural changes of the MDM2-protein remains an area to be explored. This study attempts to understand the conformational free energy and entropy costs due to this complex formation from the histograms of dihedral angles generated from molecular dynamics simulations. Residue-specific quantification illustrates that, hydrophobic residues of the protein contribute maximum to the conformational thermodynamic changes. Thermodynamic quantification of structural changes of the protein unfold the fact that, p53 binding provides a source of inter-element cooperativity among the protein secondary structural elements, where the highest affected structural elements (α2 and α4) found at the binding site of the protein affects faraway structural elements (β1 and Loop1) of the protein. The communication perhaps involves water mediated hydrogen bonded network formation. Further, we infer that in inhibitory F19A mutation of P53, though Phe19 is important in the recognition process, it has less prominent contribution in the stability of the complex. Collectively, this study provides vivid microscopic understanding of the interaction within the protein complex along with exploring mutation sites, which will contribute further to engineer the protein function and binding affinity.     

Phenanthroline-fluorescein molecular hybrid as a ratiometric and selective fluorescent chemosensor for Cu2+ via FRET strategy: synthesis,computational studies and in vitro applications

A FRET-based chemosensor L containing donor phenanthroline and acceptor fluorescein moiety was designed, synthesised and characterised for the ratiometric fluorescent detection of Cu²⁺ in organo-aqueous solution. Probe L showed high selectivity and excellent sensitivity towards Cu²⁺ ions by exhibiting both colorimetric and fluorometric changes due to opening of the spirolactum ring of fluorescein upon complexation with Cu²⁺. In presence of Cu²⁺ ions, probe L formed L-Cu²⁺ complex in 1:1 stoichiometric fashion which is established on the basis of Job’s plot and mass spectroscopy. We also performed DFT computational studies to know the binding nature and coordination feature of the complex. Furthermore, fluorescence imaging studies revealed that probe L was cell permeable and could be used to detect intracellular Cu²⁺ in living cells.     

Atomistic modeling toward high‐efficiency carbon capture: A brief survey with a few illustrative examples

With the negative environmental implications of the anthropogenic emission of greenhouse gases like CO₂ having been scientifically established, emphasis is being placed on a concerted global effort to prevent such gases from reaching the atmosphere. Especially important are capture efforts at large point emission sources like fossil fuel power generation, natural gas processing, and various industrial plants. Given the importance and scale of such activities, it is a significant priority to optimize the capture process in terms of speed, energy requirements, and cost efficiency. For CO₂ capture, in particular, multiple systems are being pursued both with near‐term retrofitting and medium‐ to long‐term designs in mind, including: (1) liquid solvents like amines, carbonates, and ionic liquids (ILs); (2) microporous sorbents like zeolites, activated carbon, and metal‐organic frameworks; (3) solid sorbents like metal‐oxides and ionic clays; and (4) polymeric and inorganic membrane separators. Each system is unique in its molecular‐level guest–host interactions, chemistry, heats of adsorption/desorption, and equilibrium thermodynamic and transport properties as a function of loading, temperature, and pressure. This opens up exciting opportunities for molecular modeling in the design and optimization of materials systems. Here, we offer a brief survey of molecular modeling applications in the field of carbon capture, with a few illustrative examples from our own work primarily involving amine solutions and ILs. Important molecular dynamics, Monte Carlo, and correlations‐based work in the literature relevant to CO₂ capture in other systems are also discussed. © 2013 Wiley Periodicals, Inc.     

Facile synthesis of substituted pyrrole-fused isocoumarins from ninhydrin

A simple and efficient procedure has been developed for the synthesis of substituted pyrrole-fused isocoumarins from easily available ninhydrin. The cyclic hemiaminal dihydroxy-indenopyrroles, the adducts of ninhydrin with enamines of acetylacetone, give pyrrole-fused isocoumarins upon heating in acidic medium. The process constitutes an interesting acid-catalyzed rearrangement to eight-membered lactams followed by intramolecular cyclization involving the amino and keto groups.     

In vitro evolution of ligands to the membrane protein caveolin

Membrane proteins comprise a third of the human genome, yet present challenging targets for reverse chemical genetics. For example, although implicated in numerous diseases including multiple myeloma, the membrane protein caveolin-1 appears to offer a poor target for the discovery of synthetic ligands due to its largely unknown structure and insolubility. To break this impasse and identify new classes of caveolae controlling lead compounds, we applied phage-based, reverse chemical genetics for the discovery of caveolin-1 ligands derived from the anti-HIV therapeutic T20. Substitution of homologous residues into the T20 sequence used a process analogous to medicinal chemistry for the affinity maturation to bind caveolin. The resultant caveolin-1 ligands bound with >1000-fold higher affinity than wild-type T20. Two types of ELISAs and isothermal titration calorimetry (ITC) measurements demonstrated high affinity binding to caveolin by the T20 variants with K(d) values in the 150 nM range. Microscopy experiments with the highest affinity caveolin ligands confirmed colocalization of the ligands with endogenous caveolin in NIH 3T3 cells. The results establish the foundation for targeting caveolin and caveolae formation in living cells.