Copper-catalyzed N-arylation of diazoles with aryl bromides using KF/Al2O3: an improved protocol

Copper-catalyzed N-arylation of diazoles can be accomplished using air-stable CuI as a copper source and 1,10-phenanthroline in the presence of KF/Al₂O₃ as a base. This is a simple and efficient method for the coupling of aryl bromide with diazoles. Different functionalized aryl bromides were coupled with diazoles using this system.     

A massively parallel electrochemical approach to the miniaturization of organic micro- and nanostructures on surfaces

This paper describes a simple and convenient strategy for reducing the dimensions of organic micro-and nanostructures on metal surfaces. By varying electrochemical desorption conditions, features patterned by dip-pen nanolithography or micro contact printing and made of linear alkanethiols or selenols can be gradually desorbed in a controlled fashion. The process is referred to as electrochemical whittling because the adsorbate desorption is initiated at the exterior of the feature and moves inward as a function of time. The whittling process and adsorbate desorption were studied as a function of substrate morphology, adsorbate head and tail groups, and electrolyte solvent and salt. Importantly, one can independently address different nanostructures made of different adsorbates and effect their miniaturization based upon ajudicious selection of adsorbate, applied potential, and supporting electrolyte. Some of the physical and chemical origins of these observations have been elucidated.     

Polymerization of methyl methacrylate in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization

Four tetradentate nitrogen ligands, viz. dichloro{[N,N^′-diphenyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (1), {[N,N^′-dioctyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (2), {[N,N^′-dibenzyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (3), and (1R,2R)-(−)-N,N^′-di(quinoline-2-methyl) di-iminocyclohexane (4), were investigated as novel complexing ligands in iron-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate where ethyl-2-bromoisobutyrate was the initiator in o-xylene at 90 °C. With ligands 1 and 2 the experimental molecular weights increased gradually with monomer conversion. High to moderate conversions (87%, 43%) were obtained in relatively short times (90 min for 1 and 30 min for 2), which indicates an efficient catalyst system, but after these times a dramatic increase in viscosity of the polymerization medium led to loss of control. It is noteworthy that polymerization proceeded in a controlled manner with ligand 1, which has two rather bulky substituents on the N-atom. Such bulky ligands did not work for a copper-based system, where they led to excessive terminations or other side reactions. When the bulkiness of the substituents was significantly increased, as in ligand 3, a decrease in polymerization rate and loss of control occurred. Ligand 4 was less efficient than the other ligands, probably because the ethylene bridge was replaced by cyclohexane bridge.     

Synthesis and pharmacological activity of 4-(4'-(chlorophenyl)-4-hydroxypiperidine) derivatives

A new series of 4-(4'-chlorophenyl)-4-hydroxypiperidine derivatives (2-5), substituted at nitrogen, were synthesized and tested as potential analgesic compounds as well as evaluated for their effect on hypotensive activity. Results showed that all the derivatives exhibit significant analgesic activity in male Wistar rats at a dose of 50 mg/kg of body weight after intramuscular injection, when tested by thermal stimuli (tail flick test). Pethidine was used as reference drug. Compounds 2, 3 and 5 produced reduction in blood pressure in normotensive rat.     

Synthesis of (R)-alpha-benzylmethionine: a novel rearrangement during alkylation of the Seebach (R)-methionine oxazolidinone

Alkylation of the enolate of the Seebach (R)-methionine oxazolidinone with benzyl bromide gave the expected benzylated product in low yield. The major product was a novel amine arising from oxazolidinone cleavage, decarboxylation, alkylation and finally hydrolysis. The rearrangement could be suppressed by using a more reactive electrophile or by using the N-Cbz instead of the N-benzoyl protecting group, and the required (R)-alpha-benzyl-methionine was obtained in 78% yield and in an enantiomeric ratio of 90:10.     

Three-stage sequential extraction procedure for metal partitioning in polluted soils and sediments

The sequential extraction procedure proposed by the Standard, Measurements and Testing program "SM&T" of the European Union has been applied to evaluate the amounts of Cr, Cu, Mn, Ni, Pb and Zn, extracted at each stage and indirectly their mobility and bioavailability in soil and sediment samples from a polluted area. Analysis of the extracts was carried out by flame atomic absorption spectrometry (FAAS). No significant matrix interferences were found except for Cr in the acetic acid and hydroxylammonium chloride extracts, which required determination by the standard additions method. Both of soils and sediments studied show similar partitioning of Mn, Ni, Cu and Cr. Mn and Ni can be considered to have significant component bound to the acido-soluble fraction, whereas, Cr and Cu occur largely in the organic and residual phases. The partitioning of Pb and Zn was different between soil and sediment. In terms of mobility and bioavailability, in soils, Ni and Mn can be regarded as moderately available followed by a lower availability of Pb while Cu, Zn and Cr have a very limited availability. In sediments, a higher availability (short-medium term) of Mn and Zn was presumed followed by a lower availability of Ni and Pb, whereas, Cu and Cr, occurring largely in the organic and residual phases, were of very limited availability.     

Electrochemically Induced Iron Release of Adsorbed Horse Spleen Ferritin: Quantitation of Iron Using Long Optical Path Length Thin‐Layer Spectroelectrochemistry

In this work, long optical path length thin‐layer electrochemical cell was constructed using indium‐tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10‐phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated.     

Correlation between Solution and the Solid State: The pH Dependent Composition in the Ternary System [Co(H2O)6]2+ or [Ni(H2O)6]2+/Piperazine/Phosphate

The protolytic equilibria of piperazine (C₄H₁₀N₂) and phosphate have been investigated in the presence of cobalt or nickel chloride or nitrate by potentiometric titrations between pH 2 and 8. Potentiometric titrations suggest the presence of [M²⁺(H₂O)₅(C₄H₁₁N₂⁺)]³⁺ and [M²⁺(H₂O)₅(C₄H₁₀N₂)]²⁺ in solution with stability constants logK of 3.1 and 3.8 for M = Co and 3.1 and 3.6 for M = Ni, respectively. Crystallization experiments were then conducted at selected pH values to isolate desired species from the known solution composition. Crystallization afforded [M(H₂O)₆]²⁺(C₄H₁₂N₂²⁺)(HPO₄^2—)₂ at pH 3.5 and 6.2 (M = Co, Ni), and Co₃(PO₄)₂·8H₂O at pH 10.5. No crystals with the dihydrogenphosphate anion or a metal‐bound piperazine ligand could be isolated under the reaction conditions. The solid‐state assembly in the isomorphous structures of [M(H₂O)₆](C₄H₁₂N₂)(HPO₄)₂ with M = Co and Ni is based on an extended hydrogen bonded network between the three ionic building blocks.     

Structural analysis of phosphatidylcholines by post-source decay matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The utility of post-source decay (PSD) matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was investigated for the structural analysis of phosphatidylcholine (PC). PC did not produce detectable negative molecular ion from MALDI, but positive ions were observed as both [PC+H](+) and [PC+Na](+). The PSD spectra of the protonated PC species contained only one fragment corresponding to the head group (m/z 184), while the sodiated precursors produced many fragment ions, including those derived from the loss of fatty acids. The loss of fatty acid from the C-1 position (sn-1) of the glycerol backbone was favored over the loss of fatty acid from the C-2 position (sn-2). Ions emanating from the fragmentation of the head group (phosphocholine) included [PC+Na-59](+), [PC+Na-183](+) and [PC+Na-205](+), which corresponded to the loss of trimethylamine (TMA), non-sodiated choline phosphate and sodiated choline phosphate, respectively. Other fragments reflecting the structure of the head group were observed at m/z 183, 146 and 86. The difference in the fragmentation patterns for the PSD of [PC+Na](+) compared to [PC+H](+) is attributed to difference in the binding of Na(+) and H(+). While the proton binds to a negatively charged oxygen of the phosphate group, the sodium ion can be associated with several regions of the PC molecule. Hence, in the sodiated PC, intermolecular interaction of the negatively charged oxygen of the phosphate group, along with sodium association at multiple sites, can lead to a complex and characteristic ion fragmentation pattern. The preferential loss of sn-1 fatty acid group could be explained by the formation of an energetically favorable six-member ring intermediate, as apposed to the five-member ring intermediate formed prior to the loss of sn-2 fatty acid group.     

Sol-gel approach to in situ creation of high pH-resistant surface-bonded organic-inorganic hybrid zirconia coating for capillary microextraction (in-tube SPME)

A novel zirconia-based hybrid organic-inorganic sol-gel coating was developed for capillary microextraction (CME) (in-tube SPME). High degree of chemical inertness inherent in zirconia makes it very difficult to covalently bind a suitable organic ligand to its surface. In the present work, this problem was addressed from a sol-gel chemistry point of view. Principles of sol-gel chemistry were employed to chemically bind a hydroxy-terminated silicone polymer (polydimethyldiphenylsiloxane, PDMDPS) to a sol-gel zirconia network in the course of its evolution from a highly reactive alkoxide precursor undergoing controlled hydrolytic polycondensation reactions. A fused silica capillary was filled with a properly designed sol solution to allow for the sol-gel reactions to take place within the capillary for a predetermined period of time (typically 15-30 min). In the course of this process, a layer of the evolving hybrid organic-inorganic sol-gel polymer got chemically anchored to the silanol groups on the capillary inner walls via condensation reaction. At the end of this in-capillary residence time, the unbonded part of the sol solution was expelled from the capillary under helium pressure, leaving behind a chemically bonded sol-gel zirconia-PDMDPS coating on the inner walls. Polycyclic aromatic hydrocarbons, ketones, and aldehydes were efficiently extracted and preconcentrated from dilute aqueous samples using sol-gel zirconia-PDMDPS coated capillaries followed by thermal desorption and GC analysis of the extracted solutes. The newly developed sol-gel hybrid zirconia coatings demonstrated excellent pH stability, and retained the extraction characteristics intact even after continuous rinsing with a 0.1 M NaOH solution for 24 h. To our knowledge, this is the first report on the use of a sol-gel zirconia-based hybrid organic-inorganic coating as an extraction medium in solid phase microextraction (SPME).