RESUMEN

The investigation of reaction mechanisms is a complex task that usually requires the use of several techniques. To obtain as much information as possible on the reaction and any intermediates - possibly invisible to one technique - the combination of techniques is a solution. In this work we present a new setup for combined UV/Vis and NMR spectroscopy and compare it to an established alternative. The presented approach allows a versatile usage of different commercially-available components like mirrors and fiber bundles as well as different fixed pathlengths according to double transmission or single transmission measurements. While a previous approach is based on a dip-probe setup for conventional NMR probes, the new one is based on a micro-Helmholtz coil array (LiquidVoxel™). This makes the use of rectangular cuvettes possible, which ensure well-defined pathlengths allowing for quantification of species. Additionally, very low quantities of compound can be analyzed due to the microfabrication and small cuvette size used. As proof-of-principle this new setup for combined UV/Vis and NMR spectroscopy is used to examine a well-studied photochromic system of the dithienylethene compound class. A thorough comparison of the pros and cons of the two setups for combined UV/Vis and NMR measurements is performed.

RESUMEN

Obtaining understanding of a photochemical reaction relies on the observation, identification and quantification of the compounds involved. The photochemical properties of the individual components are of particular importance, and their determination, however, is not always trivial. This is also true for the quantitative measure on the ability to absorb light, the extinction coefficient εi if more than one species i is present and two or more species absorb light of the same wavelength. In this work, it is demonstrated how pure component spectra can be obtained with a simple combination of successive and repeated ex situ illumination, UV/Vis and NMR spectroscopy. From the complementary information accessible, the wavelength-dependent extinction coefficients of all species can be calculated yielding the pure component spectra. A comparison with published data shows excellent agreement and thus proves that this approach is highly reliable.

RESUMEN

A supramolecular, lyotropic liquid crystalline alignment medium based on an azobenzene-containing 1,3,5-benzenetricarboxamide (BTA) building block is described and investigated. As we demonstrate, this water-based system is suitable for the investigation of various water-soluble analytes and allows for a scaling of alignment strength through variation of temperature. Additionally, alignment is shown to reversibly collapse above a certain temperature, yielding an isotropic solution. This collapse allows for isotropic reference measurements, which are typically needed in addition to those in an anisotropic environment, to be performed using the same sample just by varying the temperature. The medium described thus provides easy access to anisotropic NMR observables and simplifies structure elucidation techniques based thereon.

Asunto(s)

Cristales Líquidos , Agua , Compuestos Azo , Cristales Líquidos/química , Espectroscopía de Resonancia Magnética/métodos

RESUMEN

We present a novel concept for the in situ control of site-selectivity of catalytic acetylations of partially protected sugars using light as external stimulus and oligopeptide catalysts equipped with an azobenzene moiety. The isomerizable azobenzene-peptide backbone defines the size and shape of the catalytic pocket, while the π-methyl-l-histidine (Pmh) moiety transfers the electrophile. Photoisomerization of the E- to the Z-azobenzene catalyst (monitored via NMR) with an LED (λ = 365 nm) drastically changes the chemical environment around the catalytically active Pmh moiety, so that the light-induced change in the catalyst shape alters site-selectivity. As a proof of principle, we employed (4,6-O-benzylidene)methyl-α-d-pyranosides, which provide a change in regioselectivity from 2:1 (E) to 1:5 (Z) for the monoacetylated products at room temperature. The validity of this new catalyst-design concept is further demonstrated with the regioselective acetylation of the natural product quercetin. In situ irradiation NMR spectroscopy was used to quantify photostationary states under continuous irradiation with UV light.

RESUMEN

Lyotropic liquid crystalline phases of poly-ß-phenethylaspartates are presented as new helically chiral enantiodifferentiating alignment media with thermoresponsive properties. In addition to displaying the highest enantiodifferentiation observed for homopolypeptides, the alignment media undergo a temperature induced helix reversal without perturbing the nematic phase. This offers the opportunity to measure residual dipolar couplings (RDCs) in high and low temperature helix conformation (P- and M-helix) in one polymer. Thus different mean orientations of a chiral analyte can be determined within the same sample. Furthermore, we investigated whether the resulting media are diastereomeric and whether we are able to obtain information about the alignment process.