Interaction of chitosan and mucin in a biomembrane model environment

Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated.     

The study of the mechanical impedance of foods and biomaterials to characterize their linear viscoelastic behavior at high frequencies

A new instrumental setup, which is based on the oscillatory squeezing flow model, was developed to characterize the viscoelastic properties of foods and biopolymers. Analysis of the data was performed by two different approaches. The first approach employed principles of vibration to determine viscous damping and elasticity of the sample harmonically compressed between two plates. The second approach involved the use of additional calculations based on the squeezing flow model which were linked to concepts of vibration analysis, such as mechanical impedance, to determine fundamental rheological parameters like complex viscosity and related (elastic and viscous) moduli. The experimental setup for the method is simple to use and could be attached to existing commercial instruments such as texture analyzers and universal testing machines. The use of the proposed method with this type of instruments would provide them with the additional capability of performing dynamic rheological testing. The dynamic mass of the instrument was significantly low when compared to that of other instruments that use similar principles. This low dynamic mass enabled the use of relatively higher frequencies for the testing of the samples. Comparison of the viscous and elastic moduli obtained with the proposed method and from conventional rheometers for a variety of foods and biopolymers showed good agreements.     

Polynomial-time algorithms for regular set-covering and threshold synthesis

A set-covering problem is called regular if a cover always remains a cover when any column in it is replaced by an earlier column. From the input of the problem - the coefficient matrix of the set-covering inequalities - it is possible to check in polynomial time whether the problem is regular or can be made regular by permuting the columns. If it is, then all the minimal covers are generated in polynomial time, and one of them is an optimal solution. The algorithm also yields an explicit bound for the number of minimal covers. These results can be used to check in polynomial time whether a given set-covering problem is equivalent to some knapsack problem without additional variables, or equivalently to recognize positive threshold functions in polynomial time. However, the problem of recognizing when an arbitrary Boolean function is threshold is NP-complete. It is also shown that the list of maximal non-covers is essentially the most compact input possible, even if it is known in advance that the problem is regular.     

A selected artificial intelligence bibliography for operations researchers

We have compiled a selected, classified, and annotated Artificial Intelligence bibliography specifically addressed to an operations research audience. The bibliography includes approximately 450 references from the areas of search (including heuristics and games), automatic deduction (including theorem proving, logic programming, and logical aspects of databases), planning, learning, and knowledge-based systems (with numerous specific applications to management, engineering, science, medicine, and other fields). We have also added a general references section, as well as a special section on Artificial Intelligence/Operations Research interfaces.Supported in part by Air Force through Grant AFOSR #0271.     

Lone pair···π interactions on the stabilization of intra and intermolecular arrangements of coordination compounds with 2-methyl imidazole and benzimidazole derivatives

Abstract

Spectroscopic and single crystal X-ray diffraction studies of coordination compounds of Co^II, Ni^II, Zn^II, and Pd^II with phenylsulfonyl imidazole and benzimidazole derivatives (2-mfsiz, 2-mfsbz) were performed. The relevance of non-covalent interactions on the stabilization of intra and intermolecular arrangements in the ligands and their coordination compounds was investigated. The imidazole 2-mfsiz ligand presents two enantiomeric conformers, where the ethylphenylsulfone moiety stabilizes intermolecular lone pair···π (S–O···π_(phe)) and H···π contacts, while its tetrahedral coordination compounds, [M(2-mfsiz)₂X₂] (M²⁺?=?Co, Ni, Zn; X?=?Cl, Br) showed intramolecular lone pair···π interactions (S–O···π_(iz)). On the other hand, compounds [Cu₂(2-mfsiz)₂(µ₂-AcO)₄] and trans-[Pd(2-mfsiz)₂Cl₂] do not present lone pair···π interactions due to the metal ion geometry (square base pyramidal or square planar), which leads to formation of π_(iz)···π_(phe) interactions. For the benzimidazole ligand 2-mfsbz, an intramolecular, H_(phe)···π_(bz) contact was observed, remaining in its tetrahedral and octahedral coordination compounds, [M(2-mfsbz)₂X₂] (M²⁺?=?Co, Zn; X?=?Cl, Br, NO₃). This interaction limits the free rotation of the ethylphenylsulfone moiety for stabilization of an intermolecular lone pair···π interaction (S–O···π_(iz)). The dimeric [Zn₂(2-mfsiz)₂(µ²-AcO)₄] compound has a π_(bz)···π_(phe) contact. Theoretical calculations confirmed the non-covalent interactions in the ligands and their coordination compounds.     

A graph partition problem

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Oxidation of α-amino acids promoted by the phthalimide N-oxyl radical: A kinetic and product study

A kinetic study of the hydrogen atom transfer (HAT) reaction from a series of N-Boc- or N-Acetyl-protected amino acids to the phthalimide N-oxyl radical (PINO) was carried out to obtain information about reactivity and selectivity patterns. With amino acids containing aliphatic side chains, the 2nd order rate constants are of the same order of magnitude, in agreement with a HAT process involving the Cα?H bond. Proline is the most reactive substrate suggesting that HAT process involves the C_δ?H bond instead of C_α?H bond. These results are confirmed by the product analysis of the aerobic oxidations of the corresponding N-Boc and N-Ac protected amino acids methyl esters promoted by N-hydroxyphthalimide. Comparison of our results with those reported for HAT reactions to other radical species indicates that PINO displays electrophilic characteristics that are intermediate between those observed for the more stable Br radical and the more reactive cumyloxyl radical.     

Electron-transfer mechanism in the N-demethylation of N,N-dimethylanilines by the phthalimide-N-oxyl radical

The reactivity of the phthalimide N-oxyl radical (PINO) toward the N-methyl C-H bond of a number of 4-X-substituted N,N-dimethylanilines (X = OMe, OPh, CF(3), CO(2)Et, CN) has been investigated by product and kinetic analysis. PINO was generated in CH(3)CN by reaction of N-hydroxyphthalimide (NHPI) with Pb(OAc)(4) or, for the kinetic study of the most reactive substrates (X = OMe, OPh), with tert-butoxyl radical produced by 266 nm laser flash photolysis of di-tert-butyl peroxide. The reaction was found to lead to the N-demethylation of the N,N-dimethylaniline with a rate very sensitive to the electron donating power of the substituent (rho(+) = -2.5) as well as to the oxidation potential of the substrates. With appropriately deuterated N,N-dimethylanilines the intermolecular and intramolecular deuterium kinetic isotope effects (DKIEs) were measured for some substrates (X = OMe, CO(2)Et, CN) with the following results. First, intramolecular DKIE [(k(H)/k(D))(intra)] was found to be always different and higher than intermolecular DKIE [(k(H)/k(D))(inter)]; second, no intermolecular DKIE [(k(H)/k(D))(inter) = 1] was observed for X = OMe, whereas substantial values of (k(H)/k(D))(inter) were exhibited by X = CO(2)Et (4.8) and X = CN (5.8). These results, while are incompatible with a single step hydrogen atom transfer from the N-C-H bond to the N-oxyl radical, as proposed for the reaction of PINO with benzylic C-H bonds, can be nicely interpreted on the basis of a two-step mechanism involving a reversible electron transfer from the aniline to PINO leading to an anilinium radical cation, followed by a proton-transfer step that produces an alpha-amino carbon radical. In line with this conclusion the reactivity data exhibited a good fit with the Marcus equation and a lambda value of 37.6 kcal mol(-1) was calculated for the reorganization energy required in this electron-transfer process. From this value, a quite high reorganization energy (>60 kcal mol(-1)) is estimated for the PINO/NHPI(-H)(-) self-exchange reaction. It is suggested that the N-demethylated product derives from the reaction of the alpha-amino carbon radical with PINO to form either a cross-coupling product or an alpha-amino carbocation. Both species may react with the small amounts of H(2)O present in the medium to form a carbinolamine that, again by hydrolysis, can be eventually converted into the N-demethylated product.