Giant vesicles formed by gentle hydration and electroformation: a comparison by fluorescence microscopy

Giant unilamellar vesicles (diameter of a few tens of micrometers) are commonly produced by hydration of a dried lipidic film. After addition of the aqueous solution, two major protocols are used: (i) the gentle hydration method where the vesicles spontaneously form and (ii) the electroformation method where an ac electric field is applied. Electroformation is known to improve the rate of unilamellarity of the vesicles though it imposes more restricting conditions for the lipidic composition of the vesicles. Here we further characterize these methods by using fluorescence microscopy. It enables not only a sensitive detection of the defects but also an evaluation of the quantity of lipids in these defects. A classification of the defects is proposed and statistics of their relative importance in regard to both methods and lipid composition are presented: it shows for example that 80% of the vesicles obtained by electroformation from 98% 1,2-dioleoyl-sn-glycero-3-phosphocholine are devoid of significant defects against only 40% of the vesicles with the gentle hydration method. It is also shown that the presence of too many negatively charged lipids does not favor the formation of unilamellar vesicles with both methods. For the gentle hydration, we checked if the negatively charged lipids were inserted in the vesicles membrane in the same proportion as that of the lipid mixture from which they are formed. The constant incorporation of a negatively charged labeled lipid despite an increasing presence of negatively charged 1,2-dioleoyl-sn-glycero-3-[phospho-l-serine] tends to confirm that the composition of vesicles is indeed close to that of the initial mixture.     

Trifluoromethoxy substituted anilines: metalation as the key step for structural elaboration

Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation ("metalation") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-butyllithium at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, products 1-6. In contrast, deprotonation of the para isomer occurs at the oxygen-neighboring 3-position, giving rise to the acid 12, when the amino group is carrying two trimethylsilyl groups. sec-Butyllithium attacks 3-trifluoromethoxy-N-mono(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide respectively the acids 10 and 11 after carboxylation. The synthesis of two new benzodiazepines illustrates (19 and 22) the preparative potential of the aniline functionalization mediated by organometallic reagents.     

Reagents for new heteroannelation reactions III. 2-(Methylthio)-2-thiazoline

Summary A variety of partly novel tri- and tetracyclic hetero systems were obtained by reaction of heteroaromatic 2-aminoesters with 2-(methylthio)-2-thiazoline, yielding double-annelation of a thiazolo[2,3-b]pyrimido moiety in a one-pot process.On leave from University of Chittagong, Bangladesh     

A microcomputer-controlled titrator for automated individual analysis

A titration unit for automatic analysis systems is described. The titrator performs different titrations specified by strings of digital parameters. It has 4 independent titration stations with individual electrode systems. A multiburette with 20 cylinders provides all stations with the necessary reagents. End-point titrations, and incremental and equilibrium titrations are controlled by a microcomputer. In combination with a sample transport and a desk calculator, the titrator can be used to process automatically samples of different natures which require different treatment.     

Symmetry-adapted perturbation-theory calculations of intermolecular forces employing density-functional description of monomers

A symmetry-adapted perturbation theory based on Kohn-Sham determinants [SAPT(KS)] and utilizing asymptotically corrected exchange-correlation potentials has been applied to the He2, Ne2, (H2O)2, and (CO2)2 dimers. It is shown that SAPT(KS) is able to recover the electrostatic, first-order exchange, second-order induction, and exchange-induction energies with an accuracy approaching and occasionally surpassing that of regular SAPT at the currently programmed theory level. The use of the asymptotic corrections is critical to achieve this accuracy. The SAPT(KS) results can be obtained at a small fraction of the time needed for regular SAPT calculations. The robustness of the SAPT(KS) method with respect to the basis set size is also demonstrated. A theoretical justification for high accuracy of SAPT(KS) predictions for the electrostatic, first-order exchange, and second-order induction energies has been provided.     

Efficient desulfurization of 2-thiopyrimidine nucleosides to the corresponding 4-pyrimidinone analogues using trans-2-(phenylsulfonyl)-3-phenyloxaziridine

A brief treatment of 2-thiopyrimidine nucleosides (s²U^∗) with trans-2-phenylsulfonyl-3-phenyloxaziridine (PSO) results in efficient substrate desulfurization leading to the corresponding 4-pyrimidinone analogues (H²U^∗). The key transformation proceeds through oxidation of the 2-thiocarbonyl group to a sulfur oxyacid derivative and subsequent elimination of sulfur dioxide. 4-Pyrimidinone 1-β-d-riboside (H²U) has been transformed into the respective phosphoramidite, a ready-to-use monomer for the introduction of a modified nucleoside into an oligonucleotide chain. Moreover, the effective desulfurization of the 2-thiouridine nucleotide could be achieved directly at the oligonucleotide level, by treatment of the TdA(s²U)dGdC oligonucleotide with PSO, as verified by MALDI-TOF mass spectrometry.     

Modifying the thermosensitivity of copolymers of sodium styrene sulfonate and<Emphasis Type="Italic"> N</Emphasis>-isopropylacrylamide with dodecyltrimethylammonium chloride

The interactions between copolymers of sodium styrene sulfonate (SSS) and N-isopropylacrylamide (NIPAM), anionic polyelectrolytes, and dodecyltrimethylammonium chloride (DTAC), a cationic surfactant, were studied in aqueous solutions of various ionic strengths. The copolymers were found to be thermoresponsive, showing a lower critical solution temperature (LCST). The influence of the polymer composition, the surfactant concentration, and the ionic strength on the LCST was studied. The surfactant was found to interact strongly with the polymer, forming mixed polymer-surfactant micelles. The critical aggregation concentration (cac) of the polymer-surfactant system was found from fluorescence spectroscopy using pyrene as a fluorescent probe. A strong dependence of the anionic polyelectrolyte-cationic surfactant interactions on the structure of the ionic comonomer was observed.     

Simultaneous light emission from a mixture of dendrimer encapsulated chromophores: a model for single-layer multichromophoric organic light-emitting diodes

The site isolation of two dyes capable of electronic interaction via Forster energy transfer has been studied with the two dyes coumarin 343 and pentathiophene encapsulated by dendrons containing both solubilizing and electroactive moieties. Photoluminescence studies of mixtures of the dendritic dyes show that at high dendron generation, significant site isolation is achieved with relative emission characteristics influenced by both the degree of site isolation and the emission quantum yield of the dyes. Electroluminescence studies carried out in organic light emitting diode devices confirm that color tuning may be achieved by mixing the two encapsulated dyes in a single layer. However, selective carrier trapping by one of the core component dyes can dramatically influence the effectiveness of other components in the device.     

Generation of ortho-quinone methides upon thermal extrusion of sulfur dioxide from benzosultones

3H-1,2-Benzoxathiole 2,2-dioxides (benzosultones) undergo thermal extrusion of sulfur dioxide to form ortho-quinone methides that enter Diels-Alder reaction with maleimides to form chroman 2,3-dicarboxylic acid derivatives.