Bosons as the origin for giant magnetic properties of organic monolayers

Recently, unusual giant magnetic properties were found experimentally in some organized organic monolayers adsorbed on solid substrates. A model is presented which explains the observed phenomenon. The model is based on the special properties of electrons transferred from the substrate to the layer as a result of the adsorption process. Triplet pairing of those electrons is forced by the special 2D properties of the organic layer. Such pairs are confined within domains in the organic layer and their quantum statistics provide a model that explains the unique magnetization as well as all other features of the experimental observations. The model suggests the possible existence of Bose-Einstein condensation at room temperature on the scale of the domains.     

Synthesis and some properties of poly-(2,5-trimethylene benzimidazole) and poly-(2,5-trimethylene benzimidazole hydrochloride)

A polymer, poly(2,5-trimethylene benzimidazole), the first of a new family of nonsymmetrical polymers, was synthesized via an eight-step synthetic route. The polymer, obtained by melt polymerization, is amorphous and in its neutral form behaves as a moderate insulator. It forms 1 : 1 HCl adducts. When cast from formic acid solution, it forms 1 : 1 formic acid adducts. The acid adducts are semiconductors with resistivities in the 10⁶–10⁸ ohm-cm range. Space-charge effects are generated in the adducts as carrier mobility rises.     

Enantioselective Sulfoxidations Catalyzedby Horseradish Peroxidase, ManganesePeroxidase, and Myeloperoxidase

Summary.  Horseradish peroxidase (HRP), myeloperoxidase (MPO), and manganese peroxidase (MnP) have been shown to catalyze the asymmetric sulfoxidation of thioanisole. When H₂O₂ was added stepwise to MPO, a maximal yield of 78% was obtained at pH 5 (ee 23%), whereas an optimum in the enantiomeric excess (32%, (R)-sulfoxide) was found at pH 6 (60% yield). For MnP a yield of 18% and a high enantiomeric excess of 91% of the (S)-sulfoxide were obtained at pH 5 and a yield of 36% and an ee of 87% at pH 7.0. Optimization of the conversion catalyzed by horseradish peroxidase at pH 7.0 by controlled continuous addition of hydrogen peroxide during turnover and monitoring the presence of native enzyme as well as of intermediates I, II, and III led to the formation of the sulfoxide in high yield (100%) and moderate enantioselectivity (60%, (S)-sulfoxide). Received November 18, 1999. Accepted January 21, 2000     

Toward high-performance computational chemistry: I. Scalable Fock matrix construction algorithms

Several parallel algorithms for Fock matrix construction are described. The algorithms calculate only the unique integrals, distribute the Fock and density matrices over the processors of a massively parallel computer, use blocking techniques to construct the distributed data structures, and use clustering techniques on each processor to maximize data reuse. Algorithms based on both square and row-blocked distributions of the Fock and density matrices are described and evaluated. Variants of the algorithms are discussed that use either triple-sort or canonical ordering of integrals, and dynamic or static task clustering schemes. The algorithms are shown to adapt to screening, with communication volume scaling down with computation costs. Modeling techniques are used to characterize algorithm performance. Given the characteristics of existing massively parallel computers, all the algorithms are shown to be highly efficient for problems of moderate size. The algorithms using the row-blocked data distribution are the most efficient. © 1996 by John Wiley & Sons, Inc.     

Easily grafted polyurethanes with reactive main chain functional groups. Synthesis,characterization, and antithrombogenicity of poly(ethylene glycol)-grafted poly(urethanes)

A novel synthesis of poly(ethylene glycol) (PEG)-grafted poly(urethanes) (PURs) is described based on a precursor PUR containing free amino groups in the main chain. Three different poly(urethane) backbones were prepared: a homopoly(urethane) comprised of N-Bocdiethanolamine (BDA) and 4,4′-methylenebis(phenyl isocyanate) (MDI), a copoly(urethane) (COPUR) consisting of BDA, N-benzyldiethanolamine and MDI, and a poly(urethane urea) (PUU) that was prepared from BDA, MDI, and ethylenediamine as the chain extender. The M_n of these poly(urethanes) ranged from 32,000 to 72,000 g/mol. PEG (750, 1,900, and 5,000 g/mol) was grafted onto the boc-deprotected poly(urethanes) via the chloroformate. Films of the polymers were spin cast from dilute solutions, annealed, and the surfaces analyzed by goniometry. Water contact angle data indicates increasing PEG surface coverage of the poly(urethanes) with increasing PEG molecular weight. Reorientation of the polymer films is evidenced by contact angle hysteresis. Polymer thrombogenicity, which was studied using blood perfusion experiments, shows that COPUR-g-PEG5000 and PUU-g-PEG5000 exhibit very little platelet adhesion. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3441–3448, 1999     

Molecular mass distribution of sodium alginate by high-performance size-exclusion chromatography

A sensitive high-performance size-exclusion chromatography (HPSEC) method with simple UV detection was developed for the molecular mass analysis of sodium alginate. It was used to evaluate alginates of varying molecular mass and the results were compared with the viscosity measurements. This HPSEC method was sensitive to serve as the stability indicating method for alginate after storage under different conditions. The information of relative molecular mass distribution of alginate was provided with reference to pullulan molecular mass standards. The comparison of the HPSEC chromatograms of alginate, pullulan and dextran revealed the effect of chemical composition of a polysaccharide and its effect on apparent molecular mass distribution.     

Detection of Metal Ions (Cu2+, Hg2+) and Cocaine by Using Ligation DNAzyme Machinery

The Cu²⁺‐dependent ligation DNAzyme is implemented as a biocatalyst for the colorimetric or chemiluminescence detection of Cu²⁺ ions, Hg²⁺ ions, or cocaine. These sensing platforms are based on the structural tailoring of the sequence of the Cu²⁺‐dependent ligation DNAzyme for specific analytes. The tethering of a subunit of the hemin/G‐quadruplex DNAzyme to the ligation DNAzyme sequence, and the incorporation of an imidazole‐functionalized nucleic‐acid sequence, which acts as a co‐substrate for the ligation DNAzyme that is tethered to the complementary hemin/G‐quadruplex subunit. In the presence of different analytes, Cu²⁺ ions, Hg²⁺ ions, or cocaine, the pretailored Cu²⁺‐dependent ligation DNAzyme sequence stimulates the respective ligation process by combining the imidazole‐functionalized co‐substrate with the ligation DNAzyme sequence. These reactions lead to the self‐assembly of stable hemin/G‐quadruplex DNAzyme nanostructures that enable the colorimetric analysis of the substrate through the DNAzyme‐catalyzed oxidation of 2,2′‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonic acid), ABTS^2?, by H₂O₂ into the colored product ABTS^.?, or the chemiluminescence detection of the substrate through the DNAzyme‐catalyzed oxidation of luminol by H₂O₂. The detection limits for the sensing of Cu²⁺ ions, Hg²⁺ ions, and cocaine correspond to 1 nM , 10 nM and 2.5 μM , respectively. These different sensing platforms also reveal impressive selectivities.     

Advanced Mass Calibration and Visualization for FT-ICR Mass Spectrometry Imaging

Mass spectrometry imaging by Fourier transform ion cyclotron resonance (FT-ICR) yields hundreds of unique peaks, many of which cannot be resolved by lower performance mass spectrometers. The high mass accuracy and high mass resolving power allow confident identification of small molecules and lipids directly from biological tissue sections. Here, calibration strategies for FT-ICR MS imaging were investigated. Sub-parts-per-million mass accuracy is demonstrated over an entire tissue section. Ion abundance fluctuations are corrected by addition of total and relative ion abundances for a root-mean-square error of 0.158?ppm on 16,764 peaks. A new approach for visualization of FT-ICR MS imaging data at high resolution is presented. The ??Mosaic Datacube?? provides a flexible means to visualize the entire mass range at a mass spectral bin width of 0.001?Da. The high resolution Mosaic Datacube resolves spectral features not visible at lower bin widths, while retaining the high mass accuracy from the calibration methods discussed.