Infrared dichroism measurements on the alkyl chain packing of an ionic detergent intercalated between silicate layers

 Microcrystals of the metal silicate hydrate ilerite orient macroscopically on the surface of a ATR-crystals and thus, are accessible for infrared linear dichroism measurements. We present first results which indicate that the alkyl chain packing and the orientation of the polar group of dodecyltrimethylammoniumbromide (DTAB) intercalated between silicate layers can be determined in terms of infrared order parameters. The properties of DTAB can be modulated by the relative humidity of the surrounding atmosphere and by temperature. Upon heating DTAB undergoes a phase transition from a paraffin-like solid to a fluid phase. The former is characterized by the orthorhombic perpendicular packing of the frozen alkyl chains with tilted long axes. The interactions between the ionic groups of the surfactant and that of the host matrix stabilize the lamellar arrangement of DTAB in the crystalline and in the fluid phases. Received: 14 January 1998 Accepted: 27 July 1998     

Miniaturized sensor module for in-situ control of waters

A new sensor module is developed for the in-situ control of waters, especially surface waters. Complex miniaturized sensor technology is used for the determination of the parameters pO₂, pH, pNO₃, pCl, pPO₄, pNH₃ or pNH₄ and conductivity. Miniaturization of sensors results in small sample volumes and small volumes of calibration solution required. Results of testing this sensor module are described. The special features of this apparatus are its compact construction and its optimum functioning capability under flow conditions.     

Study of the Reactions of Platinum Macrocyclic Complex Ions with Free Radicals Formed by Pulse Radiolysis of Aqueous Media

The near-diffusion-controlled reactions of hydroxyl radical, hydrated electron, and hydrogen atom with platinum macrocyclic complex ions in aqueous media have been studied using pulse radiolysis in conjunction with UV-visible absorption and conductivity detection. The hydrated electron and hydrogen atom react with trans-[Pt(cyclam)(Cl)(2)](2+) where cyclam is 1,4,8,11-tetraazacyclotetradecane to yield platinum(III) transients that exhibit intense absorption peaks in the 280-300 nm region; however in the case of the H-atom, the reaction involves a competition between chloride abstraction and a minor process, suggested to be attack on the organic ligand. The platinum(III) products are kinetically labile toward loss of chloro ligands, but these reactions are reversible in the presence of added KCl. The reactions of hydroxyl radical with [Pt(cyclam)](2+) and with [Pt(tmc)](2+), where tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, lead to platinum(III) intermediates absorbing in the 250-300 nm region. Depending on the presence or absence of added KCl and on the pH, the platinum(III) cyclam systems can react to form a product(s) exhibiting absorption peaks near 330 and 455 nm, and this species is proposed to be a long-lived amidoplatinum(III) complex. In support of this proposal is the observation that the tmc system does not give rise to a similar visible-absorbing product. The interrelations of the cyclam-based transients through acid-base, chloro-substitution and water-elimination processes are discussed.     

Synthesis and in Vitro Evaluation of N-[[4-[2-(Carboxyl)-1-Cycloalken-1-yl]Phenyl]Methyl]Imidazoles as Nonpeptide Angiotensin II Receptor Antagonists

A series of nonpeptide angiotensin II receptor antagonists was synthesized via palladium-assisted cross coupling of aryl stannane and cycloalkenyl triflates and subsequent alkylation of silyl-protected imidazole. Our compounds, which have a terminal five- to seven-membered cycloalkenyl ring, are compared to DuPont EXP7711, an N-[(2′-carboxybiphenylyl)methyl]imidazole, which has a terminal phenyl moiety. Physicochemical properties of the compounds, such as lipophilicity, steric bulk, conformation, and the relative spatial proximity of the 2-carboxyl and the middle phenyl, are quantitated by computational chemistry. Potency in terms of binding affinity to AT₁ receptors in rat adrenal glomerulosa and rabbit aorta is maximized when the terminal ring is aromatic.     

A direct transformation of bicyclic keto esters to N-formimidoyl thienamycin

A convenient direct transformation of $\text{p}$-nitrobenzyl 6-(1′-hydroxyethyl)-1-azabicyclo-(3.2.0)heptane-3,7-dione-2-carboxylate to $\text{N}$-formimidoyl thienamycin utilizing the silylated derivative of $\text{N}$-formimidoyl cysteamine is described.     

Substituted chromans and tetrahydrofuro[2,3-b]benzofurans (trapped tetrahedral intermediates) from 3-phenyl-2-benzofuranones

The previously discovered neighboring group reaction has been extended to the synthesis of chroman derivatives (i.e., 4, 5, 6) containing geminal methyls in the 2-position, a feature common to certain physiologically active natural chromans. In two instances, cyclic ortho ester by-products (8), not observed in previous work, were formed as a result of the intramolecular trapping of tetrahedral intermediates. Reasons for the incursion of this unexpected side reaction are discussed.     

High frequency titrations involving chelation with ethylenediaminetetra-acetic acid. II. quantitative determination of some divalent metals

The high frequency oscillator provides an excellent means of detecting the end-points of titrations performed with ethylenediaminetetraacetic acid or its salts. The determination of various divalent metals is reported, based on both direct and indirect titrations. Because of the great sensitivity of the method it is possible to determine cobalt, nickel, copper (II), zinc, cadmium, lead and manganese (II) in concentration ranges of 1/1000 to 1/6000M.     

Preparation and properties of cross-linked fluorescent poly(methyl methacrylate) latex colloids

We report a single step preparation of monodisperse fluorescent poly(methyl)methacrylate (PMMA) lattices cross-linked with ethylene glycol dimethacrylate with radii in the range 150-1000 nm using dispersion polymerization. The particles are applied as fluorescent cores in core-shell PMMA particles for confocal microscopy (Dullens et al. Langmuir 2003, 19, 5963). Contrary to un-cross-linked particles, these cross-linked colloids are stable in good solvents for PMMA as well. Therefore we studied the properties of the cross-linked PMMA particles in the good solvents tetrahydrofuran (THF), chloroform, and toluene using light scattering and confocal scanning laser microscopy. We show that the particles swell instantaneously and that their volume can increase up to more than seven times their volume in poor solvents. Further, it is very likely that the particles are charged in THF.     

Synthesis of novel tri-podal mesogenic alkenes and side-chain polysiloxanes

Low molecular weight tri-podal biphenyl- and benzoate-type mesogens [C₆H₅C₆H₄O(CH₂)₅SiMe₂CH₂CH₂SiMe₂]₃CH (4), [C₁₁H₂₃O(C₆H₄)₂O(CH₂)₅SiMe₂]₃CH (5) and [MeOC₆H₄OC(O)C₆H₄O(CH₂)₅SiMe₂]₃CH (6) (C₆H₄ = 1,4-phenylene) were obtained, from branched silyl substituted methane precursors [CH₂CH(Me)₂Si]₃CH (1) and (HMe₂Si)₃CH (2). The biphenyl-containing ones (4) and (5) were converted into terminal alkenes, which were subsequently hydrosilylated with poly(methylsiloxanes). The polymer derived from (5) exhibited mesomorphic properties. Such systems have the potential to significantly increase the density of liquid crystal rod-like structures in side chains of linear polymers (or dendritic liquid crystal polymers).