Comparison of a branch-and-bound heuristic,a newsvendor-based heuristic and periodic Bailey rules for outpatients appointment scheduling systems

Appointment-based service systems admit limited number of customers at a specific time interval to make service providers more accessible by reducing customers’ waiting time and make the costly resources more productive. A traditional approach suggests the Bailey rule, which assigns one or more customers at the initial block and only one customer at remaining blocks. We prescribe two heuristic approaches and variations of the traditional Bailey rule to appointment scheduling systems with the objective of minimizing total expected costs of delay and idle times between blocks. The first heuristic adopts a branch-and-bound approach using forward dynamic programming and tries to fully enumerate with some restrictions. The second heuristic uses a sequential-inverse newsvendor approach using a starting solution. We conduct numerical tests, which show that both heuristics get near-optimal solutions in a quicker time than a commercial solver, CPLEX and that the second approach gives near-optimal solutions far faster than the first approach. In addition, we suggest the use of a periodic Bailey rule, which can be implemented easily in practice, and provides a close solution to the best result of both heuristics, depending upon cost parameters and service-time variances.     

Understanding cooperative behavior in structurally disordered populations

The effects of an inhomogeneous competing environment on the extent of cooperation are studied within the context of a site-diluted evolutionary snowdrift game on a square lattice, with the occupied sites representing the players, both numerically and analytically. The frequency of cooperation ?_C generally shows a non-monotonic dependence on the fraction of occupied sites ρ, for different values of the payoff parameter r. Slightly diluting a lattice leads to a lower cooperation for small and high values of r. For a range of r, however, dilution leads to an enhanced cooperation. An analytic treatment is developed for?_C^I + ?_C^II, with?_C^I emphasizing the importance of the small clusters of players especially for?_C^II from the other players is shown to be inadequate. A local configuration approximation (LCA) that treats the local competing configurations as the variables and amounts to include spatial correlation up to the neighborhood of a player’s neighbors is developed. Results of ?_C (ρ) and the number of different local configurations from LCA are in good agreement with simulation results. A transparent physical picture of the dynamics stemming from LCA is also presented. The theoretical approach provides a framework that can be readily applied to competing agent-based models in structurally ordered and disordered populations.     

Optimal TBHP allylic oxidation of Delta5-steroids catalyzed by dirhodium caprolactamate

Dirhodium caprolactamate is the most efficient catalyst for the oxidation of Delta5-steroids to 7-keto-Delta5-steroids by 70% tert-butyl hydroperoxide in water (T-HYDRO). Isolated product yields range from 38 to 87%.     

Ratiometric determination of Hg2+ ions based on simple molecular motifs of pyrene and dioxaoctanediamide

A new podand-type dioxaoctanediamide-based chemosensor having two pyrene moieties was prepared, and its fluoroionophoric behaviors toward transition-metal ions were investigated. Pyrene-appended dioxaoctanediamide 1 showed a selective fluorescence quenching toward Hg2+ ions over other transition-metal ions in an aqueous methanol solution. Unique responses in pyrene monomer and excimer emissions allowed selective ratiometric determination of Hg2+ ions in aqueous environments, and the detection limit was found to be 1.6 x 10(-6) M. [structure: see text]     

Prediction of molecular solvation free energy based on the optimization of atomic solvation parameters with genetic algorithm

We propose an improved solvent contact model to estimate the solvation free energy of an organic molecule from individual atomic contributions. The modification of the solvation model involves the optimization of three kinds of parameters in the solvation free energy function: atomic fragmental volume, maximum atomic occupancy, and atomic solvation parameters. All of these atomic parameters for 24 atom types are developed by the operation of a standard genetic algorithm in such a way as to minimize the difference between experimental and calculated solvation free energies. The data set for experimental solvation free energies is divided into a training set of 131 compounds and a test set of 24 compounds. Linear regressions with the optimized atomic parameters yield fits with the squared correlation coefficients (r2) of 0.89 and 0.86 for the training set and for the test set, respectively. Overall, the results indicate that the improved solvent contact model with the newly developed atomic parameters would be a useful tool for rapid calculation of molecular solvation free energies in aqueous solution.     

Continuous blood cell separation by hydrophoretic filtration

We propose a new hydrophoretic method for continuous blood cell separation using a microfluidic device composed of slanted obstacles and filtration obstacles. The slanted obstacles have a larger height and gap than the particles in order to focus them to a sidewall by hydrophoresis. In the successive structure, the height and gap of the filtration obstacles with a filtration pore are set between the diameters of small and large particles, which defines the critical separation diameter. Accordingly, the particles smaller than the criterion freely pass through the gap and keep their focused position. In contrast, the particles larger than the criterion collide against the filtration obstacle and move into the filtration pore. The microfluidic device was characterized with polystyrene beads with a minimum diameter difference of 7.3%. We completely separated polystyrene microbeads of 9 and 12 microm diameter with a separation resolution of approximately 6.2. This resolution is increased by 6.4-fold compared with our previous separation method based on hydrophoresis (S. Choi and J.-K. Park, Lab Chip, 2007, 7, 890, ref. 1). In the isolation of white blood cells (WBCs) from red blood cells (RBCs), the microfluidic device isolated WBCs with 210-fold enrichment within a short filtration time of approximately 0.3 s. These results show that the device can be useful for the binary separation of a wide range of biological particles by size. The hydrophoretic filtration as a sample preparation unit offers potential for a power-free cell sorter to be integrated into disposable lab-on-a-chip devices.     

The influence of solvent polarity and metalation on energy and electron transfer in porphyrin-phthalocyanine heterotrimers

Heteroporphyrin and -phthalocyanine arrays represent an attractive class of light harvesters and charge-separation systems exhibiting an easy route of synthesis and high chemical stability. In the present work, we report the results of photophysical investigations of two novel non-sandwich-type porphyrin-phthalocyanine heterotriads, in which two meso-tetraphenylporphyrin rings (H2TPP or ZnTPP) are linked to the central silicon atom of a silicon(IV) phthalocyanine core. It was found that the photophysical properties of the triads (H2Tr and ZnTr) in N,N-dimethylformamide (DMF) and toluene are strongly affected by two different types of interaction between the porphyrin (P) and the phthalocyanine (Pc) parts, namely excitation energy transfer (EET) and photoinduced charge transfer. The first process results in appearance of the Pc fluorescence when the P-part is initially excited, and plays a dominant role in fast depopulation of the first excited singlet state of the P moiety. If the first excited singlet state of the Pc-part is populated (either directly or via EET), it undergoes fast depopulation by hole transfer (HT) to the charge-separated (CS) state. In polar DMF, the CS state is the lowest excited state, and the charge recombination occurs directly to the ground state. Using transient absorption spectroscopy, the lifetime of the CS state was estimated to be 30 and 20 ps for H2Tr and ZnTr, respectively. In nonpolar toluene, the energy gap between the first excited singlet state of the Pc-part and the CS state is very small, and back HT occurs in both triads, resulting in appearance of "delayed fluorescence" of the Pc-part with a decay time similar to the lifetime of the CS state (190 and 280 ps for H2Tr and ZnTr, respectively). Since the energy of the CS state of ZnTr in toluene is lower than that of H2Tr, the probability of back HT for ZnTr is lower. This was clearly proved by decay-associated fluorescence spectral measurements.     

Functional insights gained from structural analyses of DNA duplexes that contain UV-damaged photoproducts

Ultraviolet photolesions endow DNA with distinct structural and dynamic properties. Biophysical studies of photoproduct-containing DNA have shown that these lesions affect the mutagenic properties of DNA and damage recognition by DNA repair systems. Recently obtained high-resolution cocrystal structures of damaged DNA bound to either DNA polymerase or DNA repair enzymes have enriched our understanding of the mechanisms by which DNA lesions are bypassed or recognized by DNA metabolizing proteins. Here, we summarize the results of these structural studies and discuss their implications for DNA metabolism.     

Expeditious synthesis of indolizine derivatives via iodine mediated 5-endo-dig cyclization

Iodine-mediated 5-endo-dig cyclization of propargylic esters 2 at room temperature proceeded smoothly to give highly functionalized indolizines 3 in excellent yields. A pyridine group was employed as a nucleophilic partner in this facile process for the first time.