Role of Surface Molecular Architecture and Energetics of Hydrogen Bonding Sites in Adsorption of Polymers and Surfactants

Hydrogen bonding is generally thought to be an ubiquitous adsorption mechanism, which often foils selective adsorption schemes. Through investigation of hydrogen bonding energy and its dependence on surface molecular architecture, it may be possible to develop new methodologies to control the adsorption of surfactants and polymeric flocculants, depressants, and dispersants used in particulate processing industries. A model system using St?ber silica spheres and polyethylene oxide, a polymer known for its ability to form hydrogen bonds, was examined. The effect of two different surface treatments of the silica particles, calcination and rehydroxylation, upon the adsorption of two polymer molecular weights was studied. The adsorption behavior was then linked to the respective surface structures via characterization of the surfaces using FTIR, NMR, and Raman techniques. In this paper role of hydrogen bonding sites and surface architecture on adsorption is discussed. Copyright 2000 Academic Press.     

Preparation of a set of selectively protected disaccharides for modular synthesis of heparan sulfate fragments: toward the synthesis of several <Emphasis Type="Italic">O</Emphasis>-sulfonated [β-D-GlcUA-(1→4)-β-D-GlcNAc]OPr types

A concise method for a stereocontrolled synthesis of a set of selectively protected disaccharides is reported. Coupling of the donor 11 onto acceptors 23 and 24, promoted by trimethylsilyl triflate-N-iodosuccinimide (TMSOTf-NIS), generated the disaccharides 25 and 26. Under typical conditions, condensation of the fully protected donor 12 onto acceptors 23 and 24 produced the disaccharides 27 and 28. The building blocks 25–28 were prepared in moderate yields having exclusive β-stereoselectivity. A unique pattern of protecting groups distinguished clearly between positions to be sulfated and functional groups remaining as free hydroxyl groups. Acetyl and/or levulinoyl esters temporarily protected the positions to be sulfated, while benzyl ethers were used for permanent protection. The anomeric positions were protected as allyl ethers, whereas the 4′-positions were masked as p-methoxybenzyl (PMB) ethers. The orthogonality of the PMB and allyl groups can then be used for further elongation of the chain by recurrent deprotection and activation steps. The hydroxyl group, OH-6, of glucosamine moieties was protected as a TBDPS ether to avoid oxidation. A five-step deprotection/sulfonation sequence was applied to the disaccharide 27 to generate the corresponding sulfated [β-D-GlcUA-2-OSO₃Na-(1→4)-β-D-Glc pNAc]-(1→O-Pro) 34.     

An efficient procedure for the synthesis of coumarin derivatives using TiCl4 as catalyst under solvent-free conditions

The ability of titanium(IV) chloride as a catalyst to promote the Pechmann condensation reaction with a range of phenols and β-keto esters is described.The reaction was carried out by addition of TiCl₄ to a mixture of the phenol and the β-keto ester with thorough stirring in the absence of a solvent and represents an improvement on the classical Pechmann conditions. The yields of coumarins obtained via this novel protocol were significantly higher than those using the conventional method and the reaction duration was reduced to a few minutes or even a few seconds.     

Strategy of analysis for the estimation of the bioavailability of zinc in foodstuffs

After the application of simulated digestive fluids (gastric and intestinale fluid) as extraction solutions, AAS and differential pulse anodic-stripping voltammetry (DPASV) were used as analytical methods in combination with ion-exchange procedures for the determination of zinc species and total zinc contents. The ion exchange procedure and the shifting of electrochemical potentials as well as changes of the calibration slope after standard addition in the polarographic analysis allowed discriminating statements with regard to a possible resorption of zinc. On the basis of these methods, a strategy is presented for in vitro investigations of the bioavailability of zinc in foodstuffs.     

Optical sensor for sulfur dioxide based on fluorescence quenching

A series of potential indicator dyes is evaluated for use in the development of optical sensors for measuring sulfur dioxide in gaseous samples. Rhodamine B isothiocyanate is selected on the basis of relative sensitivity to dynamic quenching by sulfur dioxide and oxygen. A solid-state fluorometer is described for monitoring the sulfur dioxide induced fluorescence quenching of sensing membranes composed of silicone and rhodamine B isothiocyanate. A modulated blue LED is coupled with the lock-in detection of a photodiode detector to provide high signal-to-noise ratios. The limit of detection is 0.114+/-0.009% for sulfur dioxide in a carrier stream of nitrogen gas. Selectivity measurements indicate no interference from several common gases (HCl, NH(3), NO, and CO(2)). Oxygen alters the sensor response when comparing signals for sulfur dioxide in 0, 20 and 100% oxygen environments.     

Atomic absorption spectrometric and potentiometric microdetermination of the nitro and nitroso groups in organic compounds

New simple, rapid, accurate, and selective methods are described for microdetermination of the nitro and nitroso groups in organic compounds. These are based on reduction with cadmium metal and 0.05 M HCl whereby 6 and 4 equivalents of the cadmium ions are released per nitro and nitroso groups, respectively. The cadmium ions are measured by atomic absorption spectrometry at 228.8 nm, potentiometrically by titration with EDTA using the cadmium ion selective electrode, and visually by EDTA titration using Eriochrome Black T indicator. Results with an average recovery of 98% and a mean standard deviation of 1.3% are obtainable and no interferences are caused by many nitrogen, oxygen, and sulfur functional groups.     

Synthesis of 5-Substituted 1,3-Dimethylpyrazolo[4,3-<Emphasis Type="Italic">e</Emphasis>][1,2,4]triazines

Summary.  A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines.     

Synthesis of 5-Substituted 1,3-Dimethylpyrazolo[4,3-e][1,2,4]triazines

A novel method for the synthesis of a new series of 5-substituted 1,3-dimethyl pyrazolo[4,3-e][1,2,4]triazines is described. The new synthetic strategy is based on the classical Bischler 1,2,4-benzotriazine synthesis. This approach involves the preparation of 5-hydrazinopyrazole from 5-chloro-1,3-dimethyl-4-nitropyrazole followed by acylation and nitro group reduction to form the corresponding 4-amino-3-(acylhydrazino)pyrazoles. Intramolecular oxidative cyclization of the latter derivatives, using polyphosphoric acid, produced the respective target pyrazolotriazines.     

Fused silica capillary micro-packed columns in gas chromatography

Summary Flexibility, strength and adsorption inertness of fused-silica capillaries permits their extensive application for the preparation of micro-packed columns in gas chromatography. Decreasing the column diameter (from 0.5 to 0.15 mm) and the diameter of the sorbent particles (from 100 to 5 μm) results in a marked reduction of the height equivalent to a theoretical plate (HETP), as well as in diminishing the dependence of the HETP on the carrier gas flow rate. The chromatographic characteristics of fused-silica capillary micro-packed columns and open-tubular columns are compared. The fused-silica capillary micro-packed column can be used to advantage for performing rapid and trace analyses and have been shown to be adapted for application in gas-solid chromatography. Separation of organic and inorganic compounds on fused-silica capillary micro-packed columns is illustrated by practical examples. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

A simplified sampling technique for use with the Weisz ring oven: application to qualitative analysis of some gold and silver alloys

Up to 100 microg of sample can be collected from gold or silver alloys by rubbing the specimen with the ground hemispherical tip of a 4-mm Pyrex glass rod. Gold alloys are then dissolved in potassium cyanide solution containing hydrogen peroxide; silver alloys are exposed to vapours of nitric acid. Procedures for transfer, ring oven separation and identification of alloy constituents in the sample solutions are described.