SARs of the antiprotozoal action of 6,7-diaryl-bicyclo[2.2.2]octan-2-ols

Abstract  

Several 4-amino-6,7-diarylbicyclo[2.2.2]octan-2-ols bearing varying substituents on the aromatic rings were synthesized following a manual method for applying the Hansch approach. All new compounds were tested for their activity against the causative organisms of East African sleeping sickness and malaria tropica. Structure activity relationships are discussed.     

Ultrasonic Spectrometry of Aqueous Solutions of Alkyl Maltosides: Kinetics of Micelle Formation and Head‐Group Isomerization

At frequencies between 100 kHz and 400 MHz, ultrasonic attenuation spectra are measured at 25 °C for aqueous solutions of hexyl‐, heptyl‐, octyl‐, nonyl‐, and decyl‐β‐D ‐maltopyranoside as well as of decyl‐α‐D ‐maltopyranoside. The spectra with surfactant concentration c above the relevant critical micelle concentration (cmc) display three relaxation terms with discrete relaxation times. That with a relaxation time between 0.1 and 1.2 μs is due to exchange of monomers between micelles and the suspending phase. It is discussed in the light of the Teubner–Kahlweit–Aniansson–Wall model of the formation/decay kinetics of systems with Gaussian size distribution of micelles. The relaxation parameters are compared to those for solutions of other non‐ionic surfactants, such as alkyl monoglycosides and poly(ethylene glycol) monoalkyl ethers. At c<cmc this low‐frequency relaxation term is missing and at c≈cmc it is broadened, as is characteristic of solutions of oligomeric molecular structures rather than proper micelles. The relaxation terms with relaxation times between 6 and 15 ns and 0.7 and 2.3 ns reveal head‐group rotations around glycosidic angles and isomerization of the exocyclic hydroxymethyl group, respectively. These unimolecular reactions are also examined with a view to solutions of alkyl monoglycosides as well as of glucose and maltose.     

The use of acetone as a substitute for acetonitrile in analysis of peptides by liquid chromatography/electrospray ionization mass spectrometry

The recent worldwide shortage of acetonitrile has prompted interest in alternative solvents for liquid chromatography/mass spectrometry (LC/MS). In this work, acetone was substituted for acetonitrile in the separation of a peptide mixture by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) and in the positive electrospray ionization mass spectrometry (ESI‐MS) of individual peptides. On both C12 and C18 stationary phases, the substitution of acetone for acetonitrile as the organic component of the mobile phase did not alter the gradient elution order of a five‐peptide retention standard, but did increase peak width, shorten retention times, and increase peak tailing. Positive ESI mass spectra were obtained for angiotensin I, bradykinin, [Leu⁵]‐enkephalin, and somatostatin 14 dissolved in both acetonitrile/water/formic acid (25%/75%/0.1%) and acetone/water/formic acid (25%/75%/0.1%). Under optimized ESI‐MS conditions, the mass spectral response of [Leu⁵]‐enkephalin was increased two‐fold when the solvent contained acetone. The substitution of acetone for acetonitrile resulted in only slight changes in the responses of the remaining peptides. A higher capillary voltage was required for optimum response when acetone was used. Compared with acetonitrile/water/formic acid (50/50/0.1%), more interfering species below m/z = 140 were found in the ESI‐MS spectra of acetone/water/formic acid (50/50/0.1%). Copyright © 2009 John Wiley & Sons, Ltd.     

XNBR/LDH nanocomposites: Effect of vulcanization and organic modifier on nanofiller dispersion and strain‐induced crystallization

In elastomer/organo clay nanocomposites, the morphological characteristics, and hence the mechanical properties, of the vulcanizates are strongly influenced by the organic modifier and the vulcanization process. When the elastomer itself undergoes strain‐induced crystallization, both the organic modifier and the dispersed filler particles could significantly influence the crystallization process. These phenomena are very common in case of natural rubber‐based vulcanizates. In this study, the similar effects have been demonstrated with carboxylated nitrile rubber (XNBR) and organically modified layered double hydroxide (O‐LDH)‐based nanocomposites. The effect of size of the organic modifier was obviously visible on the interlayer distance of O‐LDH and also on the morphological reorganization of the dispersed O‐LDH particles during vulcanization process. The strain‐induced crystallization of the XNBR was found to be strongly dependent on the morphological change that occurs during vulcanization process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Capillary Electrophoresis Coupled On-Line with Nitrogen-Selective Thermionic Detection Using an Eluent-Jet Interface

The on-line coupling of capillary electrophoresis (CE) with a thermionic detector (TID) originally developed for gas chromatography (GC) is reported for the first time. An eluent-jet interface previously used to combine micro-liquid chromatography and mass spectrometry can now be used to couple CE and TID. Preliminary results demonstrate the possibility of performing direct nitrogen-selective detection, even for less volatile compounds. Detection limits of 4–12 pg N/s were obtained for the four tested compounds piperidine, dimethylformamide, tetra-n-butylammonium hydroxide, and nicotinic acid. Optimization of both the TID and the eluent-jet interface can be performed independently; optimum TID parameters agree rather closely with the detector specifications under GC conditions. The nitrogen-selective TID proved to be linear over more than three orders of magnitude with acceptable repeatability. The on-line coupling of CE and TID may well become an interesting approach for the rapid and direct analysis of ionic and high-molecular-mass N-containing compounds.     

Thermolysis of 1-(1-aryl-1-bromomethyl)cyclopropyl bromides: a reinvestigation

Two compounds, the (Z)- and (E)-isomers of 2,4-dibromo-1-p-tolyl-1-butene 2a and 3a, respectively, were isolated in 65% total yield when 1-(1-bromo-1-p-tolylmethyl)cyclopropyl bromide (1a) was heated at 150 degrees C for 1 h. 1,1-Dibromo-2-p-tolylcyclobutane (4a), previously reported to be the only product in this reaction, was not detected. The phenyl analogue of 1a reacted similarly and gave the (Z)- and (E)-isomers of 2,4-dibromo-1-phenyl-1-butene 2b and 3b, respectively, in 60% yield. A rationale for the reaction is presented.     

The copolymerization of propylene with higher,linear α‐olefins

Propylene was copolymerized with the linear α‐olefins 1‐octene, 1‐decene, 1‐tetradecene, and 1‐octadecene. The metallocene catalyst Me₂Si(2‐Me Benz[e]Ind)₂ZrCl₂, in conjunction with methylalumoxane as a cocatalyst, was used to synthesize the copolymers. The copolymers were characterized by ¹³C and ¹H NMR with a solvent mixture of 1,2,4‐trichlorobenzene (TCB) and benzene‐d₆ (9/1) at 100 °C. Thermal analyses were carried out to determine the melting and crystallization temperatures, whereas the molecular weights and molecular weight distributions were determined by gel permeation chromatography with TCB at 140 °C. Glass‐transition temperatures were determined with dynamic mechanical analysis. Relationships among the comonomer type and amount of incorporation and the melting/crystallization temperatures, glass‐transition temperature, crystallinity, and molecular weight were established. Moreover, up to 3.5% of the comonomer was incorporated, and there was a decrease in the molecular weight with increased comonomer content. Also, the melting and crystallization temperatures decreased as the comonomer content increased, but this relationship was independent of the comonomer type. In contrast, the values for the glass‐transition temperature also decreased with increased comonomer content, but the extent of the decrease was dependent on the comonomer type. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4110–4118, 2000     

C,C‐ and N,C‐Coupled Dimers of 2‐Aminotetraphenylporphyrins: Regiocontrolled Synthesis,Spectroscopic Properties,and Quantum‐Chemical Calculations

β,β′‐Bisporphyrins are intrinsically chiral porphyrin dimers with fascinating properties. The configurational stability at their axes can be directed by variation of the central metal atoms. Herein, we present a regioselective functionalization of the monomeric 2‐amino‐tetraphenyl‐porphyrin as a versatile substrate for dimerization by oxidative coupling. By simple variation of the reaction conditions (solvent and oxidant), the oxidation selectively gave either the axially chiral C,C‐coupled diaminobisporphyrin in high yields or, under Ullmann conditions, the twofold N,C‐linked achiral dimer, also in good yields. A generalized mechanism for the coupling reaction is proposed based on DFT calculations. The axially chiral β,β′‐coupled porphyrin dimers were isolated as racemic mixtures, but can be resolved by HPLC on a chiral phase. TDDFT and coupled‐cluster calculations were used to explain the spectroscopic properties of the aminoporphyrins and their dimers and to elucidate the absolute configurations of the C,C‐coupled bisporphyrins.