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1.
Proc Natl Acad Sci U S A ; 119(15): e2111989119, 2022 04 12.
Artículo en Inglés | MEDLINE | ID: mdl-35377781

RESUMEN

Understanding the evaporation process of binary sessile droplets is essential for optimizing various technical processes, such as inkjet printing or heat transfer. Liquid mixtures whose evaporation and wetting properties may differ significantly from those of pure liquids are particularly interesting. Concentration gradients may occur in these binary droplets. The challenge is to measure concentration gradients without affecting the evaporation process. Here, spectroscopic methods with spatial resolution can discriminate between the components of a liquid mixture. We show that confocal Raman microscopy and spatially resolved NMR spectroscopy can be used as complementary methods to measure concentration gradients in evaporating 1-butanol/1-hexanol droplets on a hydrophobic surface. Deuterating one of the liquids allows analysis of the local composition through the comparison of the intensities of the C­H and C­D stretching bands in Raman spectra. Thus, a concentration gradient in the evaporating droplet was established. Spatially resolved NMR spectroscopy revealed the composition at different positions of a droplet evaporating in the NMR tube, an environment in which air exchange is less pronounced. While not being perfectly comparable, both methods­confocal Raman and spatially resolved NMR experiments­show the presence of a vertical concentration gradient as 1-butanol/1-hexanol droplets evaporate.

2.
J Am Chem Soc ; 146(1): 170-180, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38117177

RESUMEN

The kinetic resolution of trans-cyclohexane-1,2-diol with a lipophilic oligopeptide catalyst shows extraordinary selectivities. To improve our understanding of the factors governing selectivity, we quantified the Gibbs free energies of interactions of the peptide with both enantiomers of trans-cyclohexane-1,2-diol using nuclear magnetic resonance (NMR) spectroscopy. For this, we use advanced methods such as transverse relaxation (R2), diffusion measurements, saturation transfer difference (STD), and chemical shift (δ) analysis of peptide-diol mixtures upon varying their composition (NMR titrations). The methods employed give comparable and consistent results. The molecular recognition by the catalyst is approximately 3 kJ mol-1 in favor of the preferentially acetylated (R,R)-enantiomer in the temperature range studied. Interestingly, the difference of 3 kJ mol-1 is also confirmed by results from reaction monitoring of the acylation step under catalytic conditions, indicating that this finding is true regardless of whether the investigation is performed on the acetylated species or on the free catalyst. To arrive at these conclusions, the self-association of both the catalyst and the substrate in toluene was found to play an important role and thus needs to be taken into account in reaction screening.

3.
Chemistry ; 30(23): e202304016, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38360972

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.

4.
J Am Chem Soc ; 145(6): 3615-3623, 2023 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-36749116

RESUMEN

Two polyaspartates bearing ortho-fluorinated azobenzenes (pFAB) as photo-responsive groups in the side chain were synthesized: PpFABLA (1) and co-polyaspartate PpFABLA-co-PBLA [11, 75%(n/n) PpFABLA content]. As a consequence of the E/Z-isomerization of the side chain, PpFABLA (1) undergoes a visible-light-induced reversible coil-helix transition in solution: Green light (525 nm) affords the coil, and violet light (400 nm) affords the helix. pFAB significantly increases the thermal stability of the Z-isomer at 20 °C (t1/2 = 66 d for the Z-isomer) and effectively counters the favored back formation of the helix. At 20%(w/w) polymer concentration, the helical polymer forms a lyotropic liquid crystal (LLC) that further orients unidirectionally inside a magnetic field, while the coil polymer results in an isotropic solution. The high viscosity of the polymer solution stabilizes the coexistence of liquid crystalline and isotropic domains, which were obtained with spatial control by partial light irradiation. When used as an alignment medium, PpFABLA (1) enables (i) the measurement of dipolar couplings without the need for a separate isotropic reference and (ii) the differentiation of enantiomers. PpFABLA-co-PBLA (11) preserves the helical structure, by intention, independently of the E/Z-isomerization of the side chain: Both photo-isomers of PpFABLA-co-PBLA (11) form a helix that─at a concentration of 16%(w/w)─form an LLC. Despite the absence of a change in the secondary structure, the E/Z-isomerization of the side chain changes the morphology of the liquid crystal and leads to different sets of dipolar coupling for the same probe molecule.

5.
J Am Chem Soc ; 145(29): 15912-15923, 2023 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-37409501

RESUMEN

The Pd-catalyzed allylic alkylation of 3,4-disubstituted, racemic cyclobutene electrophiles exhibits a highly unusual stereoselectivity that allows for controlling diastereo- and enantioselectivity only by the choice of ligand and independent of the configuration of the substrate. In order to shed light on the origin of stereoinduction, we performed a systematic mechanistic investigation, including preparation of various putative Pd-allyl intermediates, 1H/31P NMR reaction monitoring, 2H-labeling studies, ESI-HRMS and 31P NMR analysis of reaction mixtures, and DFT structural computations. The mechanism disclosed exhibits several steps with stereospecificities deviating from the commonly accepted "double inversion rule": oxidative addition was found to follow a stereoconvergent course, giving anti-configured η1-Pd-cyclobutene species as detectable on-cycle intermediates irrespective of the configuration of starting material, while the subsequent nucleophilic attack features a stereodivergent behavior. In stark contrast to their highly reactive anti-analogues, syn-Pd-cyclobutene complexes that can be formed as side products are rendered entirely unreactive by strong internal Pd-O chelation, preventing the formation of undesired product diastereomers.

6.
J Org Chem ; 2023 Jan 19.
Artículo en Inglés | MEDLINE | ID: mdl-36655948

RESUMEN

Inherently chiral compounds, such as calixarenes, are chiral due to a nonplanar three-dimensional (3D) structure. Determining their conformation is essential to understand their properties, with nuclear magnetic resonance (NMR) spectroscopy being one applicable method. Using alignment media to measure residual dipolar couplings (RDCs) to obtain structural information is advantageous when classical NMR parameters like the nuclear Overhauser effect (NOE) or J-couplings fail. Besides providing more accurate structural information, the alignment media can induce different orientations of enantiomers. In this study, we examined the ability of polyglutamates with different side-chain moieties─poly-γ-benzyl-l-glutamate (PBLG) and poly-γ-p-biphenylmethyl-l-glutamate (PBPMLG) ─to enantiodifferentiate the inherently chiral phenoxathiin-based thiacalix[4]arenes. Both media, in combination with two solvents, allowed for enantiodiscrimination, which was, to the best of our knowledge, proved for the first time on inherently chiral compounds. Moreover, using the experimental RDCs, we investigated the calix[4]arenes conformational preferences in solution, quantitatively analyzed the differences in the alignment of the enantiomers, and discussed the pitfalls of the use of the RDC analysis.

7.
Photochem Photobiol Sci ; 22(11): 2599-2606, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37751073

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.

8.
Magn Reson Chem ; 60(6): 563-571, 2022 06.
Artículo en Inglés | MEDLINE | ID: mdl-35266585

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
9.
Soft Matter ; 17(10): 2849-2856, 2021 Mar 18.
Artículo en Inglés | MEDLINE | ID: mdl-33585845

RESUMEN

Circular dichroism (CD) spectroscopy is commonly used for investigation of the secondary structure of biomolecular compounds as well as polymers in isotropic solution. In anisotropic solution, the usage of the apparent CD is prone to misinterpretations due to artefacts from contributions of e.g. linear dichroism (LD). Herein, a method for the complete cancelation of anisotropic artefacts in the apparent CD is developed and its validity proven. The approach is further used for investigation of the conformation and the lyotropic liquid crystalline (LLC) structure of a copolyaspartate. For this system, a temperature-dependent change of the polymer's helical conformation (helix reversal) is known. Furthermore, a rotation of the aligned polymer helices inside a magnetic field (helix realignment) is independently present, occurring at a lower temperature compared to the helix reversal. In the current study, the helix reversal is confirmed and found to be accompanied by a change of the LLC structure. A cholesteric structure is detected and revealed to change its sense (cholesteric reversal) at the temperature at which the helix realigns in the magnetic field. The determination of the cholesteric sense is enabled by measuring the induced CD of an achiral dye, dissolved in the anisotropic polymer solution. Investigation of the anisotropic polymer solution is, thus, only made possible by cancellation of the aforementioned anisotropic artefacts. This allows the observation of changes of the liquid crystal structure from right-handed cholesteric, through left-handed cholesteric, to nematic with increasing temperature.


Asunto(s)
Artefactos , Péptidos , Dicroismo Circular , Soluciones
10.
J Org Chem ; 86(21): 15387-15402, 2021 11 05.
Artículo en Inglés | MEDLINE | ID: mdl-34677977

RESUMEN

Residual dipolar couplings (RDCs) become increasingly important as additional NMR parameters in the structure elucidation of organic compounds but are usually used in fitting procedures to discriminate between (computed) structures that are in accordance with RDCs and others that can be ruled out. Thus, the determination of configurations requires prior structural information. The direct use of RDCs as restraints to construct structures based on RDCs has only recently begun also in organic compounds. No protocol has been published though that uses the vector and dynamics information available in multialignment data sets directly for the joint determination of conformation and configuration of organic compounds. This is proposed in the current study. We show that by employing these data, even a flat or random start structure converges into the correctly configured structure when employing multiple alignment data sets in our iterative procedure. The requirements in terms of the number of RDCs and alignment media necessary are discussed in detail.


Asunto(s)
Compuestos Orgánicos , Espectroscopía de Resonancia Magnética , Conformación Molecular , Resonancia Magnética Nuclear Biomolecular , Titanio
11.
Phys Chem Chem Phys ; 24(1): 281-286, 2021 Dec 22.
Artículo en Inglés | MEDLINE | ID: mdl-34881759

RESUMEN

Residual dipolar couplings (RDCs) contain information on the relative arrangement and dynamics of internuclear spin vectors in chemical compounds. Classically, RDC data is analyzed by fitting to structure models, while model-free approaches (MFA) directly relate RDCs to the corresponding internuclear vectors. The recently introduced software TITANIA implements the MFA and extracts structure and dynamics parameters directly from RDCs to facilitate de novo structure refinement for small organic compounds. Encouraged by our previous results on simulated data, we herein focus on the prerequisites and challenges faced when using purely experimental data for this approach. These concern mainly the fact that not all couplings are accessible in all media, leading to voids in the RDC matrix and the concomitant effects on the structure refinement. It is shown that RDC data sets obtained experimentally from currently available alignment media and measurement methods are of sufficient quality to allow relative configuration determination even when the relative configuration of the analyte is completely unknown.

12.
Angew Chem Int Ed Engl ; 60(38): 21040-21046, 2021 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-34259370

RESUMEN

The application of anisotropic parameters in NMR-spectroscopy enables the acquisition of spatial and angular information, complementary to those from conventional isotropic NMR-measurements. The use of alignment media is a well-established method for inducing anisotropy. PBPMLG is a recently discovered polyglutamate-based alignment medium, exhibiting thermoresponsive behavior in the lyotropic liquid crystalline (LLC) phase, thus offering potential for deeper understanding of the alignment process. We present one approach for investigating the thermoresponsive behavior by synthesizing specifically deuterated PBPMLG-isotopologues and their subsequent analyses using 2 H NMR-spectroscopy. It was possible to relate the observed thermoresponsive behavior to a flip of the polymer with respect to the external magnetic field-an effect never observed before in glutamate-based polymeric alignment media. Furthermore, a solvent-induced temperature dependent gelation was verified in THF, which might provide yet another opportunity to manipulate the properties of this alignment medium in the future.

13.
Chemistry ; 26(35): 7831-7839, 2020 Jun 23.
Artículo en Inglés | MEDLINE | ID: mdl-32134524

RESUMEN

Residual dipolar couplings (RDCs) offer additional information for structure elucidation by NMR spectroscopy. They are measured in anisotropic media, such as lyotropic liquid crystalline phases of polypeptides. Today, some suitable polypeptides are known. Nevertheless, structural influences of these polypeptides on the alignment properties are not really understood. Thus, which influence a chiral side chain has on enantiodiscrimination and whether we can improve the enantiodifferentiation significantly by adding an additional chiral center in the side chain are questions of interest. Therefore, new diastereomeric polypeptide-based alignment media with an additional chiral center in the side chain derived from perillyl alcohol were synthesized and their properties were investigated (secondary structure, liquid crystallinity, etc.). The enantiomers of isopinocampheol and ß-pinene were used as model analytes for the study of enantiodiscrimination. Additionally, the usage of 1 H-1 H-RDCs to improve the alignment tensor quality is demonstrated.

14.
J Org Chem ; 85(4): 1835-1846, 2020 02 21.
Artículo en Inglés | MEDLINE | ID: mdl-31763833

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.

15.
Angew Chem Int Ed Engl ; 59(13): 5316-5320, 2020 03 23.
Artículo en Inglés | MEDLINE | ID: mdl-31945235

RESUMEN

Residual dipolar couplings (RDCs) are amongst the most powerful NMR parameters for organic structure elucidation. In order to maximize their effectiveness in increasingly complex cases such as flexible compounds, a maximum of RDCs between nuclei sampling a large distribution of orientations is needed, including sign information. For this, the easily accessible one-bond 1 H-13 C RDCs alone often fall short. Long-range 1 H-1 H RDCs are both abundant and typically sample highly complementary orientations, but accessing them in a sign-sensitive way has been severely obstructed due to the overflow of 1 H-1 H couplings. Here, we present a generally applicable strategy that allows the measurement of a large number of 1 H-1 H RDCs, including their signs, which is based on a combination of an improved PSYCHEDELIC method and a new selective constant-time ß-COSY experiment. The potential of 1 H-1 H RDCs to better determine molecular alignment and to discriminate between enantiomers and diastereomers is demonstrated.

16.
Soft Matter ; 15(20): 4192-4199, 2019 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-31065653

RESUMEN

Elastin-like peptides are biopolymers that display LCST behaviour in solution quite similar to other synthetic polymers like polyethylene oxide. Here we study the structure of the peptide GVG(VPGVG)3 in a temperature range of 25 °C to 70 °C with small angle neutron scattering. The LCST for this peptide is outside the experimental range of temperatures. Molecular conformation is well described within the model of a random coil but increasing temperature leads to significant changes. The peptide displays a combination of conformational change and aggregation that show up in the scattering at low and intermediate scattering vector q. The aggregate size is determined from an integral measure of the scattered intensity. It increases with temperature and concentration. For low concentration we find a size variation with temperature that may be related to the collapse of conformation at the inverse temperature transition (ITT).


Asunto(s)
Elastina/química , Péptidos Cíclicos/química , Enlace de Hidrógeno , Peso Molecular , Agregado de Proteínas , Conformación Proteica , Temperatura , Temperatura de Transición
17.
Metab Eng ; 46: 20-27, 2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-29466700

RESUMEN

Plants are versatile chemists producing a tremendous variety of specialized compounds. Here, we describe the engineering of entirely novel metabolic pathways in planta enabling generation of halogenated indigo precursors as non-natural plant products. Indican (indolyl-ß-D-glucopyranoside) is a secondary metabolite characteristic of a number of dyers plants. Its deglucosylation and subsequent oxidative dimerization leads to the blue dye, indigo. Halogenated indican derivatives are commonly used as detection reagents in histochemical and molecular biology applications; their production, however, relies largely on chemical synthesis. To attain the de novo biosynthesis in a plant-based system devoid of indican, we employed a sequence of enzymes from diverse sources, including three microbial tryptophan halogenases substituting the amino acid at either C5, C6, or C7 of the indole moiety. Subsequent processing of the halotryptophan by bacterial tryptophanase TnaA in concert with a mutant of the human cytochrome P450 monooxygenase 2A6 and glycosylation of the resulting indoxyl derivatives by an endogenous tobacco glucosyltransferase yielded corresponding haloindican variants in transiently transformed Nicotiana benthamiana plants. Accumulation levels were highest when the 5-halogenase PyrH was utilized, reaching 0.93 ±â€¯0.089 mg/g dry weight of 5-chloroindican. The identity of the latter was unambiguously confirmed by NMR analysis. Moreover, our combinatorial approach, facilitated by the modular assembly capabilities of the GoldenBraid cloning system and inspired by the unique compartmentation of plant cells, afforded testing a number of alternative subcellular localizations for pathway design. In consequence, chloroplasts were validated as functional biosynthetic venues for haloindican, with the requisite reducing augmentation of the halogenases as well as the cytochrome P450 monooxygenase fulfilled by catalytic systems native to the organelle. Thus, our study puts forward a viable alternative production platform for halogenated fine chemicals, eschewing reliance on fossil fuel resources and toxic chemicals. We further contend that in planta generation of halogenated indigoid precursors previously unknown to nature offers an extended view on and, indeed, pushes forward the established frontiers of biosynthetic capacity of plants.


Asunto(s)
Carmin de Índigo/metabolismo , Nicotiana/metabolismo , Plantas Modificadas Genéticamente/metabolismo , Plantas Modificadas Genéticamente/genética , Nicotiana/genética
18.
Chemistry ; 24(58): 15631-15637, 2018 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-30085366

RESUMEN

The use of anisotropic NMR parameters-especially residual dipolar couplings (RDCs)-offers access to additional structural information and, therefore, alignment media required for this approach are under a continuous development. Here, we present poly-γ-p-biphenylmethyl-glutamate (PBPMG) as a new versatile enantiodifferentiating alignment medium. The thermoresponsive properties of this polymer allowed for RDC measurements of more than one orientation within the same sample at different temperatures. Moreover, the outstanding enantiodifferentiation along with excellent spectral quality even offered the opportunity to differentiate enantiomers in mixtures.

19.
Chemistry ; 24(54): 14373-14377, 2018 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-29999196

RESUMEN

Poly(aspartic acid esters) are known to form either right-or left-handed α-helices depending on the ester group in the side chain, on solvent and/or on temperature. Polyphenethyl-l-aspartates (PPLA) exhibit a helix reversal from the right- to the left-handed form with increasing temperature. We have recently reported the application of polyphenethylaspartates as helically chiral alignment media. The thermoresponsivity observed for these polymers offers the possibility to measure different orientations of analytes before and after helix reversal of the alignment medium at 373 K. Herein we present a synthesized copolymer of phenethyl- and benzylaspartate as a new alignment medium undergoing this helix reversal at 303-313 K. Thus, the measurement of residual dipolar couplings (RDC) before and after the helix reversal is allowed for at ambient temperatures. A complete sign change of all 1 H-13 C RDCs was observed, which is close to the highest possible difference in NMR spectra.


Asunto(s)
Ácido Aspártico/análogos & derivados , Ácido Aspártico/química , Espectroscopía de Resonancia Magnética/métodos , Poliésteres/química , Temperatura , Anisotropía , Conformación Molecular , Solventes , Termodinámica
20.
Chemistry ; 24(2): 492-498, 2018 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-29095539

RESUMEN

NMR spectroscopy with in situ irradiation uncovered unique photoswitchable intramolecular hydrogen bonds (IMHBs) in 5-phenylazopyrimidines with two hydrogen bond donors. These compounds form two stable rotamers, each with one IMHB, and the rotamer ratio changes reversibly upon UV or visible light irradiation. Strong substituent dependence of photoinduced structural changes was observed; using suitable substituents, orthogonal photoswitching can be achieved. For example, whereas UV irradiation caused switching between the two rotamers of the trans isomer of a compound with electron-donating methoxy substituent, visible light enabled to obtain the cis photoisomer. No cis isomer was detected for compounds with electro-neutral or electron-accepting substituents, but photoswitching between the two trans isomers was observed. On the other hand, compounds without hydrogen-bond donors or with one donor only formed stable cis isomers. A mechanism of the photoswitching was proposed by DFT computations.

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