Preparation and characterization of n-alkanoic acid self-assembled monolayers adsorbed on 316L stainless steel

The electrochemical formation and characterization of decanoic, myristic, palmitic, and stearic acid self-assembled monolayers on a native oxide surface of 316L stainless steel have been studied. This work describes a new approach to surface modification of stainless steel in which the self-assembly of n-alkanoic acids is facilitated by applying a potential to the stainless steel in an organic electrolyte solution. While decanoic acid forms a disorganized monolayer as a result of sweeping the potential in an acetonitrile solution containing 0.1 mM of the respective acid, longer acids, that is, myristic and palmitic acids, form highly ordered closed-packed monolayers. This electrochemical approach results in highly reproducible monolayers that are deposited within a shorter time than the traditional assembly process. The monolayers were characterized by cyclic voltammetry, double-layer capacity (ac voltammetry), contact angle measurements, X-ray photoelectron spectroscopy, and external reflection-absorption Fourier transform infrared spectroscopy. The utilization and implications of this modification technique are discussed.     

Determination of selected neurotransmitter metabolites using monolithic column chromatography coupled with chemiluminescence detection

The oxidation of selected clinically important neurotransmitter metabolites with acidic potassium permanganate in the presence of polyphosphates evokes chemiluminescence of sufficient intensity to enable the sensitive determination of these species. Limits of detection for 5-hydroxyindole-3-acetic acid (5-HIAA), vanilmandelic acid (VMA; α,4-dihydroxy-3-methoxybenzeneacetic acid), 4-hydroxy-3-methoxyphenylglycol (MHPG), homovanillic acid (HVA, 4-hydroxy-3-methoxyphenylacetic acid) and 3,4-dihydroxyphenylacetic acid (DOPAC) were between 5 × 10⁻⁹ and 4 × 10⁻⁸ M, using flow-injection analysis methodology. In addition, we demonstrate the rapid determination of homovanillic acid and 5-hydroxyindole-3-acetic acid in human urine - without the need for extraction procedures - using monolithic column chromatography with chemiluminescence detection.     

Electron transfer from dibenzo[b,f]-1-azapentalene dianion: Attempted synthesis of dibenzo[b,f]-1-azapentalene

When dibenzo[b,f]-1-azapentalene dianion (3) was allowed to react with either iron (III) chloride or ethylene bromide, a one-electron transfer from3 took place readily to give the radical anion11. Further electron transfer from11 did not occur presumably due to the antiaromatic character of dibenzo[b,f]-1-azapentalene (1) that would have resulted. The radical anion11 underwent further transformation by hydrogen abstraction from the solvent to give 5,10-dihydroindeno[1,2-b]indole (2) and by dimerization to themeso and (R,S) isomers of 5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indole (4 a and4 b) respectively.

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Elektronentransfer von Dibenzo[b,f]-1-azapentalen-Dianion: Ein Versuch zur Synthese von Dibenzo[b,f]-1-azapentalen

Zusammenfassung Die Reaktion von Dibenzo[b,f]-1-azapentalen-Dianion (3) mit Eisen (III) oder Ethylenbromid ergab einen Ein-Elektronentransfer zum Radikalanion11. Ein weiterer Elektronentransfer fand nicht statt, vermutlich wegen des antiaromatischen Charakters von Dibenzo[b,f]-1-azapentalen (1), das dabei entstehen müßte. Das Radikalanion11 ergab unter Wasserstoffentzug aus dem Lösungsmittel 5,10-Dihydroindeno[1,2-b]indol (2), das weiter zummeso- bzw. (R,S)-5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indol (4 a bzw.4 b) dimerisierte.

     

Efficiency in integral facility design problems

An example of design might be a warehouse floor (represented by a setS) of areaA, with unspecified shape. Givenm warehouse users, we suppose that useri has a known disutility functionf _isuch thatH _i(S), the integral off _iover the setS (for example, total travel distance), defines the disutility of the designS to useri. For the vectorH(S) with entriesH _i(S), we study the vector minimization problem over the set {H(S) :S a design} and call a design efficient if and only if it solves this problem. Assuming a mild regularity condition, we give necessary and sufficient conditions for a design to be efficient, as well as verifiable conditions for the regularity condition to hold. For the case wheref _iis thel _p-distance from warehouse docki, with 1<p<, a design is efficient if and only if it is essentially the same as a contour set of some Steiner-Weber functionf =₁ f ₁++ _m f _m ,when the _i are nonnegative constants, not all zero.This research was supported in part by the Interuniversity College for PhD Studies in Management Sciences (CIM), Brussels, Belgium; by the Army Research Office, Triangle Park, North Carolina; by a National Academy of Sciences-National Research Council Postdoctorate Associateship; and by the Operations Research Division, National Bureau of Standards, Washington, D.C. The authors would like to thank R. E. Wendell for calling Ref. 16 to their attention.     

Synthesis of PI3K inhibitor GDC-0077 via a stereocontrolled N-arylation of α-amino acids

An efficient synthesis of PI3K inhibitor GDC-0077, featuring two consecutive Cu-catalyzed CN coupling reactions, is reported. The described synthetic route involves a chemoselective Ullmann-type coupling of a chiral difluoromethyl-substituted oxazolidinone, a Cu-catalyzed N-arylation of l-alanine with high stereochemical integrity, and a high-yielding final amide bond formation step to produce GDC-0077 in >99.5 area % HPLC purity.     

THE EXCITATION OF 8-METHOXYPSORALEN WITH VISIBLE LIGHT: REVERSED PHASE HPLC QUANTITATION OF MONOADDUCTS and CROSS-LINKS

Abstract— The formation of 8-methoxypsoralen-DNA monoadducts and cross-links is presumed to be responsible for the efficacy of photochemotherapies that employ 8-methoxypsoralen activated with long-wavelength ultraviolet radiation (UVA,320–400 nm). In this report it is shown that 8-methoxypsoralen can also be activated with visible light (419 nm). Bovine aorta smooth muscle cells were treated with 8-methoxypsoralen (1000 ng/mL) and 419 nm light (up to 12 J/cm²). Cellular DNA was isolated, hydrolyzed using nucleolytic enzymes and then analyzed by reversed-phase high-performance liquid chromatography. The primary effect of using visible light instead of long-wavelength ultraviolet radiation is a more than 10-fold reduction in the extent of cross-link formation. Because the extent of monoadduct and cross-link formation has not been routinely measured in experiments in which cellular assays have been performed, it is difficult to correlate cell response to the presence of a particular type of 8-methoxypsoralen photoadduct (monoadduct or cross-link). Thus, the use of visible light allows the study of cells containing nearly 100% monoadducts. In addition, the reduction in cross-link formation when visible light is used to activate the compound may also reduce the mutagenicity of 8-methoxypsoralen and hence enhance its therapeutic efficacy.     

New heterodimetallic cyclopentadienyl carbonyl complexes: crystal structure of (C5Me4Et)(μ-CO)3Ru(C5Me5)

A series of heterodimetallic complexes of general formula (C₅R₅)M(μ-CO)₃RuC₅Me₅ (M = Cr, Mo, W; R = Me, Et) has been prepared in good yields by the reaction of [C₅R₅M(CO)₃]⁻ with [C₅Me₅Ru(CH₃CN)₃]⁺. (C₅Me₄Et)W(μ-CO)₃Ru(C₅Me₅) was characterized by a crystal structure determination. The W---Ru bond length of 2.41 Å is consistent with the formulation of a metal-metal triple bond, while the unsymmetrical bonding mode of the three bridging carbonyl groups reflects the inherent non-equivalence of the two different C₅R₅M-units. Using [CpRu(CH₃CN)₃]⁺ or [CpRu(CO)₂(CH₃CN)]⁺ as the cationic precursor leads to the formation of dimetallic species (C₅R₅)M(CO)₅RuC₅H₅ with both bridging and terminal carbonyl groups.     

An approach to estimate the energy and strength of the intramolecular hydrogen bond in different conformers of 4‐methylamino‐3‐penten‐2‐one

The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Diglycidyl ether of bisphenol-A epoxy resin–polyether sulfone/polyether sulfone ether ketone blends: phase morphology, fracture toughness and thermo-mechanical properties

The properties of diglycidyl ether of bisphenol-A epoxy resin toughened with poly(ether sulfone ether ketone) (PESEK) and poly(ether sulfone) (PES) polymers were investigated. PESEK was synthesised by the nucleophilic substitution reaction of 4,4’-difluorobenzophenone with dihydroxydiphenylsulfone using sulfolane as solvent and potassium carbonate as catalyst at 230 °C. The T _g–composition behaviour of the homogeneous epoxy resin/PESEK blend was modelled using Fox, Gordon–Taylor and Kelley–Bueche equations. A single relaxation near the glass transition of epoxy resin was observed in all the blend systems. From dynamic mechanical analysis, the crosslink density of the blends was found to decrease with increase in the thermoplastic concentration. The storage modulus of the epoxy/PESEK blends was lower than that of neat resin, whilst it is higher for epoxy/PES blends up to glass transition temperature, thereafter it decreases. Scanning electron microscopic studies of the blends revealed a homogeneous morphology. The homogeneity of the blends was attributed to the similarity in chemical structure of the modifier and the cured epoxy network and due to the H-bonding interactions between the blend components. The fracture toughness of epoxy resin increased on blending with PESEK and PES. The increase in fracture toughness was due to the increase in ductility of the matrix. The thermal stability of the blends was comparable to that of neat epoxy resin.