Search results for "SoMe"

Synthesis of all-syn Functionalized Triphenylene Ketals

2011

The stereoselective synthesis of triphenylene ketals offers access to unique scaffolds. For a good performance in supramolecular applications an all-syn orientation of the functional groups is essential. The oxidative trimerization of catechol ketals by molybdenum pentachloride or mixtures with titanium tetrachloride leads to a template-directed formation. Several heterocyclic moieties are suitable for this transformation. A template-directed isomerization of anti,anti,syn isomers to the desired C 3 -symmetric derivative was demonstrated in two cases.

Tandem Reactions of 1,2,4-Oxadiazoles with Allylamines

2011

A reaction of 3-chloro-1,2,4-oxadiazoles with allylamine and diallylamine has been investigated. 3,3a,4,5-Tetrahydroisoxazolo[3,4-d]pyrimidines are produced through a tandem ANRORC/[3 + 2]cycloaddition pathway consisting of the addition of allylamine to the 1,2,4-oxadiazole, followed by ring opening, nitrone formation, and finally cycloaddition. 3-N-Allylamino-1,2,4-oxadiazoles were also obtained as minor products through a classical SNAr. Conversely, a reaction with diallylamine produces 3-N,N-diallylamino-1,2,4-oxadiazole and imidazoline through tandem SNAr/aziridination and nucleophilic ring opening.

From Polymers to Nanomedicines: New Materials for Future Vaccines

2013

Nanomedicine is the medical application of nanotechnology and therefore covers various kinds of nanoparticles. In this chapter, we would like to provide a brief introduction and overview of nanoparticles for the modulation of the immune system. In general, these nano-sized objects can be inorganic colloids, organic colloids (synthesized by emulsion polymerization or mini-/nanoemulsion techniques), polymeric aggregates (micelles or polymersomes), core cross-linked aggregates (nanohydrogels, crosslinked micelles, or polyplexes), multifunctional polymer coils, dendritic polymers or perfect dendrimers. A special focus is set on polymeric materials, because the chemical composition of the partic…

2021

Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with alpha-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C6F5)(3) groups attached to the CN- ligands stabilize t…

Modified photobehavior of carboxylic acid derivatives induced by protonation

1987

Abstract A series of carboxylic acid derivatives 1–6 containing a second interacting function have been converted into the corresponding O -protonated species or acylium ions upon treatment with 96% sulfuric acid or oleum, respectively, at room temperature. The resulting stable cations have been spectroscopically characterized and submitted to irradiation. Cis-trans photoisomerization was observed in the ionic speciesderived from trans -crotonic, fumaric and maleic acids, and maleic anhydride. By contrast protonated crotonolactone 5a+ was found to be photostable. Finally, protonated α-bromobutyrolactone 6a+ was clean and efficiently dehydrohalogenated to 5a+ upon irradiation. Since the norm…

Polymer-induced shape changes and capping in giant liposomes

1995

We studied the coupling of a polymeric amphiphile undergoing a transition from an expanded to a collapsed state of the hydrophilic polymer chain upon heating above 29°C with free and solid supported lipid bilayers. Lateral diffusion measurements and studies of vesicle shape-changes confirmed previous calorimetric studies, suggesting that the amphiphile remains incorporated in the giant vesicles and the supported bilayer during the transition. The two-dimensional hydrodynamic radii of the amphiphile in the expanded and collapsed state was measured by making use of the strong quadratic dependence of the diffusion coefficient on the radius of the diffusant (D ∞ r−2) due to the frictional coupl…

On the handedness of helical aggregates of C3 tricarboxamides: a multichiroptical characterization

2015

A complete chiroptical characterization of the supramolecular polymers formed by tricarboxamides (S)-1 and (R)-1 is performed using ECD, VCD and CPL dichroic techniques. The helical aggregates show an intense CPL signal and their absolute P- or M-configuration is assigned with the help of theoretical calculations.

Photoswitchable coordination compounds

2001

Photoswitchable compounds represent an attractive class of materials in coordination chemistry. Recent progress dealing with transition metal compounds involving photo-induced changes of the magnetic and/or optical properties to long-lived metastable states are covered in the present review article. The basic photophysical phenomena together with representative examples such as nitroprusside derivatives, relevant spin crossover complexes, stilbenoid complexes and finally Prussian blue analogues are discussed. Some possible applications regarding energy and information storage are suggested at the end.

Biomolecular-solvent stereodynamic coupling probed by deuteration.

1983

Thermodynamic interpretation of experiments with isotopically perturbed solvent supports the view that solvent stereodynamics is directly relevant to thermodynamic stability of biomolecules. According with the current understanding of the structure of the aqueous solvent, in any stereodynamic configuration of the latter, connectivity pathways are identifiable for their topologic and order properties. Perturbing the solvent by isotopic substitution or, e.g., by addition of co-solvents, can therefore be viewed as reinforcing or otherwise perturbing these topologic structures. This microscopic model readily visualizes thermodynamic interpretation. In conclusion, the topologic stereodynamic str…

EFFECTS OF DIETARY 18:3 N-3 TRANS ISOMERS ON THE ?6 DESATURATION OF ?-LINOLENIC ACID

1995

Trans isomers of polyunsaturated fatty acids (PUFA) are formed during heat treatment of oils. In the present work, the effect of dietary geometrical isomers of α-linolenic acid (18:3 n-3) on the Δ6 desaturation of all cis 18:3 n-3 was investigated, using rat liver microsomes. The desaturation rates were higher in microsomes from animals fed a cis n-3 deficient diet, as compared to those from the control group or those from rats fed 18:3 n-3 and its trans isomers. These data and the incorporation of long chain trans PUFA in microsomal lipids suggest that geometrical isomers of 18:3 n-3 are probably slowly desaturated and elongated into long chain trans polyunsaturated fatty acids compared to…