One-carbon homologation of carboxylic acids via BtCH(2)TMS: a safe alternative to the Arndt--Eistert reaction

Carboxylic acids are converted into the corresponding homologated acids or esters, using easily available 1-(trimethylsilylmethyl)benzotriazole (1) as a one-carbon synthon. The effectiveness of the reaction has been investigated on six aryl and seven alkyl carboxylic acids.     

Orthogonal, convergent syntheses of dendrimers based on melamine with one or two unique surface sites for manipulation

An orthogonal, convergent route for the introduction of substoichiometric numbers of latent surface sites into dendrimers based on melamine is used to prepare targets that display one or two Boc-protected amines on the periphery. Asymmetry is the result of the stepwise incorporation of functionalized and unfunctionalized dendrons onto the triazine cores, a highly selective process due to the different reactivities of the substituted triazines. The routes to the dendrons rely on iterative reactions of the growing dendrons with triazine cores and diamine linkers. p-Aminobenzylamine is used as a linking group to avoid functional group interconversions or protecting group manipulations. Addition of the benzylamine group to the monochlorotriazine of the dendron proceeds cleanly leaving a less reactive aniline for subsequent reaction with trichlorotriazine. The routes to these targets proceed in 5 or 6 linear steps (11 or 12 total steps) in 40% overall yield. The unique surface sites can be deprotected and subjected to additional chemistries. Reaction of the monofunctionalized dendrimer with trichlorotriazine yields the desired dimer, a molecule whose increased size is evident from light scattering and tapping mode atomic force microscopy, and corroborated with computation.     

Analysis of combinatorial chemistry samples by micellar electrokinetic chromatography

A micellar electrokinetic chromatography (MEKC) method has been developed that can evaluate the purity of samples generated in combinatorial chemistry libraries. This method uses an open tube capillary (27 cm x 50 microm) along with a run buffer composed of sodium dodecyl sulfate (SDS), hydroxypropyl-beta-cyclodextrin, and sodium tetraborate coupled with UV detection. Neutral compounds and compounds that were insoluble in aqueous buffers could be analyzed under these conditions in approximately 3 min. The concentration of SDS and the concentration of hydroxypropyl-beta-cyclodextrin effected the separation. The affect on selectivity resulting from the addition of an organic modifier to the run buffer was examined. The low background absorbency of the run buffer made for easy detection of compounds that absorbed at low UV wavelengths. The quick analysis time made this suitable for analysis of combinatorial chemistry samples.     

Analysis of acyclovir by high performance capillary electrophoresis with on-column amperometric detection

The separation of acyclovir (ACV) by high performance capillary electrophoresis (HPCE) with on-column amperometric detection using alpha-amino-5-mercapto-3,4-dithiazole (AMD) as internal standard is described. The calibration line was linear in the range of 0.5-20 mg/L of ACV. The detection limit was 0.15 mg/L of ACV. Its recovery ranged from 98 to 101% with relative standard deviations (RSDs) from 1.9 to 3.2% (n = 5). This method was successfully used for determining ACV in some pharmaceuticals and human urine. Comparable results with HPCE with ultraviolet (UV) detection and amperometric detection were obtained.     

Effects of matrix-assisted laser desorption/ionization experimental conditions on quantitative compositional analysis of ethylene oxide/propylene oxide copolymers

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has the potential to become a valuable tool for the compositional analysis of copolymers. For a copolymer composed of structurally very similar building blocks with minor chain length changes, one would expect the relative peak intensities observed in the MALDI mass spectra to reflect its composition, at least within a narrow mass range. However, we show that variations in experimental conditions in MALDI can have a significant effect on the mass spectral appearance of a copolymer. The effects of concentration, laser power, type of matrices and solvents on mass spectra of an ethylene oxide/propylene oxide copolymer are illustrated. These somewhat surprising results show that great care needs to be exercised when interpreting copolymer spectra for compositional analysis, even for copolymers with structurally similar monomers. This work also points out that further studies are needed to better understand and optimize spectral acquisition conditions for reliable copolymer compositional analysis by MALDI.     

LIGHT-SCATTERING STUDY OF POLYELECTROLYTE HOLLOW CAPSULES

Silver halide (AgX) microcrystal was used as template to synthesize hollow polyelectrolyte capsules. These hollow capsules were characterized by laser light scattering (LLS) used to measure the size of the capsules in solution. The ratio of hydrodynamic radius (Rh) from dynamic LLS to the radius of gyration (Rg) from static LLS is almost unity, revealing that the entities are hollow in solution. The results suggest that the LLS method can be regarded as a good complement to the confocal laser scanning microscopy (CLSM) method for the characterization of small hollow capsules, and it possesses the advantage of not needing fluorescence labeling.     

Chiral separation of anticholinergic drug enantiomers in nonaqueous capillary electrophoresis

Nonaqueous capillary electrophoretic (NACE) method for the separation of nine structurally similar chiral anticholinergic drugs was developed. The eight drug enantiomers were separated on baseline within 18 min using 20mM phosphoric acid and 10 mM NaOH, containing 10 mM heptakis(2,3-dimethyl-6-sulfato)-4beta-cyclodextrin (HDMS-beta-CD) in methanol. The results were compared with those obtained in the high performance liquid chromatography system.     

Bridged bis-pyridinylimino dinickel(II) complexes: Syntheses, characterization, ethylene oligomerization and polymerization

A series of bridged bis(pyridinylimino) ligands were efficiently synthesized through the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) with 2-pyridinecarboxaldehyde or 2-benzoylpyridine. They reacted with (DME)NiBr₂ to form dinuclear Ni(II) complexes. All resultant compounds were characterized by elemental analysis, IR spectra as well as the single-crystal X-ray diffraction to confirm the structures of ligands and complexes. Activated with methylaluminoxane (MAO), these nickel complexes showed considerably good activities for ethylene oligomerization and polymerization. Their catalytic activities and the properties of PEs obtained were depended on the arched environment of ligand and reaction conditions.     

ADSORPTION OF 2,4-DICHLOROBENZOXYACETIC ACID ONTO HYPERCROSSLINKED RESIN MODIFIED BY PHENOLIC HYDROXYL GROUP (AM-1)

INTRODUCTIONAdsorption has been considered to be the best available technology for removing organics from water in the USSafe Drinking Water Act[1]. Due to many drawbacks of activated carbon[2-7], the most widely used adsorbent,hypercrosslinked polymeric adsorbents developed by Tsyurupa and Davankov[8] have been increasingly viewedas an alternative to activated carbon for selective removal of specific organic substances from contaminatedwater[9-12], and series of researches have been do…