A 'microfluidic pinball' for on-chip generation of Layer-by-Layer polyelectrolyte microcapsules

Inspired by the game of "pinball" where rolling metal balls are guided by obstacles, here we describe a novel microfluidic technique which utilizes micropillars in a flow channel to continuously generate, encapsulate and guide Layer-by-Layer (LbL) polyelectrolyte microcapsules. Droplet-based microfluidic techniques were exploited to generate oil droplets which were smoothly guided along a row of micropillars to repeatedly travel through three parallel laminar streams consisting of two polymers and a washing solution. Devices were prototyped in PDMS and generated highly monodisperse and stable 45±2 μm sized polyelectrolyte microcapsules. A total of six layers of hydrogen bonded polyelectrolytes (3 bi-layers) were adsorbed on each droplet within <3 minutes and a fluorescent intensity measurement confirmed polymer film deposition. AFM analysis revealed the thickness of each polymer layer to be approx. 2.8 nm. Our design approach not only provides a faster and more efficient alternative to conventional LbL deposition techniques, but also achieves the highest number of polyelectrolyte multilayers (PEMs) reported thus far using microfluidics. Additionally, with our design, a larger number of PEMs can be deposited without adding any extra operational or interfacial complexities (e.g. syringe pumps) which are a necessity in most other designs. Based on the aforementioned advantages of our device, it may be developed into a great tool for drug encapsulation, or to create capsules for biosensing where deposition of thin nanofilms with controlled interfacial properties is highly required.     

The stable set problem and the lift-and-project ranks of graphs

We study the lift-and-project procedures for solving combinatorial optimization problems, as described by Lovász and Schrijver, in the context of the stable set problem on graphs. We investigate how the procedures' performances change as we apply fundamental graph operations. We show that the odd subdivision of an edge and the subdivision of a star operations (as well as their common generalization, the stretching of a vertex operation) cannot decrease the N₀-, N-, or N₊-rank of the graph. We also provide graph classes (which contain the complete graphs) where these operations do not increase the N₀- or the N-rank. Hence we obtain the ranks for these graphs, and we also present some graph-minor like characterizations for them. Despite these properties we give examples showing that in general most of these operations can increase these ranks. Finally, we provide improved bounds for N₊-ranks of graphs in terms of the number of nodes in the graph and prove that the subdivision of an edge or cloning a vertex can increase the N₊-rank of a graph.Research of these authors was supported in part by a PREA from Ontario, Canada and research grants from NSERC.Mathematics Subject Classification (2000): 0C10, 90C22, 90C27, 47D20     

New polyphenylene‐g‐polystyrene and polyphenylene‐g‐polystyrene/poly(ε‐caprolactone) copolymers by combined controlled polymerization and cross‐coupling processes

1,4‐Dibromo‐2‐(bromomethyl)benzene and 1,3‐dibromo‐5‐(bromomethyl)benzene were used as initiators in the atom transfer radical polymerization of styrene in conjunction with CuBr/2,2′‐bipyridine as a catalyst. The resulting polystyrene (PSt)‐based macromonomers, possessing at one end a 2,5‐dibromophenylene or 3,5‐dibromophenylene moiety, were used in combination with 2,5‐dihexylbenzene‐1,4‐diboronic acid for Suzuki coupling in the presence of Pd(PPh₃)₄ as a catalyst or with the system NiCl₂/2,2′‐bipyridine/triphenylphosphine/Zn for Yamamoto polymerization. Polyphenylenes (PPs) with PSt chains as substitution groups were obtained. The same macromonomers were used in Yamamoto copolycondensation reactions, in combination with a poly(ε‐caprolactone) (PCL) macromonomer, and this resulted in PPs with PSt/PCL side chains. The obtained PPs had good solubility properties in common organic solvents at room temperature similar to those of the starting macromonomers. The new polymers were characterized with ¹H (¹³C) NMR, IR, and gel permeation chromatography. The optical properties of the polymers were monitored with UV and fluorescence spectroscopy. The thermal behaviors of the macromonomers and final PPs were investigated with differential scanning calorimetry and compared. The morphology of PPs containing PSt and PCL blocks was characterized with atomic force microscopy, and a microphase‐separated layered morphology was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 879–896, 2005     

Tuning the surface hydrophobicity of polymer/nanoparticle composite films in the Wenzel regime by composition

Surface hydrophobicity of composite films containing polymer and nanoparticles has been studied as a function of composition. We show that the hydrophobicity can be tuned by adjusting the amount of particles in the two-component system. A sharp transition from a polymer-rich surface to a nanoparticles-rich surface was observed with increasing mass fraction of particles in spin-coated thin films. Water drops on the films did not slide down even at tilt angles of 90 degrees . Contact angle hysteresis increased with the mass fraction of particles indicating that the surface roughness increased as the surfaces remained in the Wenzel regime. Contact angle hysteresis data were quantitatively consistent with predictions of a recent theory.     

X-ray photoelectron spectroscopic investigation of conducting polymer blends

Electrochemically prepared films of conducting polymers of polypyrrole and polythiophene and their blends with polyamide have been investigated by X-ray photoelectron spectroscopy. In the N1s region of the spectra of films containing polypyrrole the peak corresponding to N⁺ at 402.0 eV is separated from that of neutral N. The intensity of the N⁺ peak can be correlated with the electrical conductivity of the films and the spectroscopically derived ratio of F/N⁺ is close to 4 indicating that one BF^-₄ dopant ion is incorporated for every oxidized nitrogen center. In the spectra of films of polythiophene and its blends peaks corresponding to S and S⁺ can not be resolved but again the F/C ratio correlates with the electrical conductivity.     

Rhodium-catalyzed carbonylative arylation of alkynes with arylboronic acids: an efficient and straightforward method in the synthesis of 5-aryl-2(5H)-furanones

5-Aryl-2(5H)-furanones can be synthesized by the Rh-catalyzed reactions of arylboronic acids with internal alkynes under a CO atmosphere.     

Admission control for a multi-server queue with abandonment

In a M/M/N+M queue, when there are many customers waiting, it may be preferable to reject a new arrival rather than risk that arrival later abandoning without receiving service. On the other hand, rejecting new arrivals increases the percentage of time servers are idle, which also may not be desirable. We address these trade-offs by considering an admission control problem for a M/M/N+M queue when there are costs associated with customer abandonment, server idleness, and turning away customers. First, we formulate the relevant Markov decision process (MDP), show that the optimal policy is of threshold form, and provide a simple and efficient iterative algorithm that does not presuppose a bounded state space to compute the minimum infinite horizon expected average cost and associated threshold level. Under certain conditions we can guarantee that the algorithm provides an exact optimal solution when it stops; otherwise, the algorithm stops when a provided bound on the optimality gap is reached. Next, we solve the approximating diffusion control problem (DCP) that arises in the Halfin–Whitt many-server limit regime. This allows us to establish that the parameter space has a sharp division. Specifically, there is an optimal solution with a finite threshold level when the cost of an abandonment exceeds the cost of rejecting a customer; otherwise, there is an optimal solution that exercises no control. This analysis also yields a convenient analytic expression for the infinite horizon expected average cost as a function of the threshold level. Finally, we propose a policy for the original system that is based on the DCP solution, and show that this policy is asymptotically optimal. Our extensive numerical study shows that the control that arises from solving the DCP achieves a very similar cost to the control that arises from solving the MDP, even when the number of servers is small.     

Determining the Zn Content of Cherry in Field Using VNIR Spectroscopy

Visible and near-infrared(VNIR)spectroscopy is an eco-friendly method used for estimating plant nutrient deficiencies.The aim of this study was to investigate the possibility of using VNIR method for estimating Zn content in cherry orchard leaves under field conditions.The study was conducted in 3different locations in Isparta region of Turkey.Fifteen cherry orchards containing normal and Zn deficient plants were chosen,and 60 leaf samples were collected from each location.The reflectance spectra of the leaves were measured with an ASD FieldSpec HandHeld spectroradiometer and a plant probe.The Zn contents of leaf samples were predicted through laboratory analysis.The spectral reflectance measurements were used to estimate the Zn levels using stepwise multiple linear regression analysis method.Prediction models were created using the highest coefficient of determination value.The results show that Zn content of cherry trees can be estimated using the VNIR spectroscopic method(87.5相似文献   

Isometries between completely regular vector-valued function spaces

Periodica Mathematica Hungarica - In this paper, first we study surjective isometries (not necessarily linear) between completely regular subspaces A and B of $$C_0(X,E)$$ and $$C_0(Y,F)$$ where X...     

A Constant-Potential Infeasible-Start Interior-Point Algorithm with Computational Experiments and Applications

We present a constant-potential infeasible-start interior-point (INFCP) algorithm for linear programming (LP) problems with a worst-case iteration complexity analysis as well as some computational results.The performance of the INFCP algorithm is compared to those of practical interior-point algorithms. New features of the algorithm include a heuristic method for computing a good starting point and a procedure for solving the augmented system arising from stochastic programming with simple recourse. We also present an application to large scale planning problems under uncertainty.