Dr. Benjamin Koeppe
Profil
Forschungsthemen1
Entwicklung von molekularen Photoschaltern zur effektiven Steuerung des pH-Werts wässriger Lösungen durch sichtbares Licht
Quelle ↗Förderer: DFG Eigene Stelle (Sachbeihilfe) Zeitraum: 08/2015 - 10/2018 Projektleitung: Dr. Benjamin Koeppe
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Stand: 26.4.2026, 19:48:44 (Top-K=20, Min-Cosine=0.4)
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Publikationen25
Top 25 nach Zitationen — Quelle: OpenAlex (BAAI/bge-m3 embedded für Matching).
Journal of the American Chemical Society · 75 Zitationen · DOI
Combined low-temperature NMR/UV-vis spectroscopy (UVNMR), where optical and NMR spectra are measured in the NMR spectrometer under the same conditions, has been set up and applied to the study of H-bonded anions A··H··X(-) (AH = 1-(13)C-2-chloro-4-nitrophenol, X(-) = 15 carboxylic acid anions, 5 phenolates, Cl(-), Br(-), I(-), and BF(4)(-)). In this series, H is shifted from A to X, modeling the proton-transfer pathway. The (1)H and (13)C chemical shifts and the H/D isotope effects on the latter provide information about averaged H-bond geometries. At the same time, red shifts of the π-π* UV-vis absorption bands are observed which correlate with the averaged H-bond geometries. However, on the UV-vis time scale, different tautomeric states and solvent configurations are in slow exchange. The combined data sets indicate that the proton transfer starts with a H-bond compression and a displacement of the proton toward the H-bond center, involving single-well configurations A-H···X(-). In the strong H-bond regime, coexisting tautomers A··H···X(-) and A(-)···H··X are observed by UV. Their geometries and statistical weights change continuously when the basicity of X(-) is increased. Finally, again a series of single-well structures of the type A(-)···H-X is observed. Interestingly, the UV-vis absorption bands are broadened inhomogeneously because of a distribution of H-bond geometries arising from different solvent configurations.
Angewandte Chemie International Edition · 56 Zitationen · DOI
A head of the game: A new probe head for simultaneous NMR and UV/Vis spectroscopic measurements is designed. 1H NMR and UV/Vis spectra of an intermolecular hydrogen-bonded complex (see scheme) are measured simultaneously in CD2Cl2 at 175 K. Aided by the 1H NMR spectra, the sample concentration can be adjusted so that the desired complex is the exclusive form of the phenol present. The UV/Vis spectra allow the approximate position of the bridging proton to be found.
The Journal of Physical Chemistry A · 54 Zitationen · DOI
We explore the N-H stretching vibrations of adenosine-thymidine base pairs in chloroform solution with linear and nonlinear infrared spectroscopy. Based on estimates from NMR measurements and ab initio calculations, we conclude that adenosine and thymidine form hydrogen bonded base pairs in Watson-Crick, reverse Watson-Crick, Hoogsteen, and reverse Hoogsteen configurations with similar probability. Steady-state concentration and temperature dependent linear FT-IR studies, including H/D exchange experiments, reveal that these hydrogen-bonded base pairs have complex N-H/N-D stretching spectra with a multitude of spectral components. Nonlinear 2D-IR spectroscopic results, together with IR-pump-IR-probe measurements, as also corroborated by ab initio calculations, reveal that the number of N-H stretching transitions is larger than the total number of N-H stretching modes. This is explained by couplings to other modes, such as an underdamped low-frequency hydrogen-bond mode, and a Fermi resonance with NH(2) bending overtone levels of the adenosine amino-group. Our results demonstrate that modeling based on local N-H stretching vibrations only is not sufficient and call for further refinement of the description of the N-H stretching manifolds of nucleic acid base pairs of adenosine and thymidine, incorporating a multitude of couplings with fingerprint and low-frequency modes.
Angewandte Chemie International Edition · 52 Zitationen · DOI
Under pressure: Carboxylic acid dimers enclosed in molecular capsules experience an internal pressure of about 5–10 kbar, which leads to compression of the hydrogen bonds (see scheme). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
The Journal of Physical Chemistry A · 51 Zitationen · DOI
The wavelength dependence of the photochemistry of anthracene-9,10-endoperoxide (APO) in acetonitrile was quantitatively investigated at 5 °C, with excitation varied from 240 to 450 nm. Anthracene (AC) and a diepoxide (DE) were identified as the main primary photoproducts. After short exposure times DE was at all wavelengths the dominating photoproduct, while AC was only formed for λ ≤ 320 nm. The maximum AC quantum yield of 29% was reached at 270 nm. Anthraquinone (AQ) and a bicyclic acetal (BA) were identified as the main secondary products. Formation of AQ and BA occurred both from DE and from ground-state APO. Formation of BA from ground-state APO involved excited DE or BA itself, while formation of BA from DE required UV excitation of DE. Room-temperature thermolysis of APO only produced AQ. For λ ≤ 310 nm the total photochemistry quantum yield was, within error margins, constant and close to unity. Between 300 and 450 nm, the tail of the APO absorption spectrum, a more or less monotonic decrease of the total photochemistry quantum yield was observed.
Journal of the American Chemical Society · 50 Zitationen · DOI
Heteroconjugated hydrogen-bonded anions A···H···X(-) of phenols (AH) and carboxylic/inorganic acids (HX) dissolved in CD2Cl2 and CDF3/CDF2Cl have been studied by combined low-temperature UV-vis and (1)H/(13)C NMR spectroscopy (UVNMR). The systems constitute small molecular models of hydrogen-bonded cofactors in proteins such as the photoactive yellow protein (PYP). Thus, the phenols studied include the PYP cofactor 4-hydroxycinnamic acid methyl thioester, and the more acidic 4-nitrophenol and 2-chloro-4-nitrophenol which mimic electronically excited cofactor states. It is shown that the (13)C chemical shifts of the phenolic residues of A···H···X(-), referenced to the corresponding values of A···H···A(-), constitute excellent probes for the average proton positions. These shifts correlate with those of the H-bonded protons, as well as with the H/D isotope effects on the (13)C chemical shifts. A combined analysis of UV-vis and NMR data was employed to elucidate the proton transfer pathways in a qualitative way. Dual absorption bands of the phenolic moiety indicate a double-well situation for the shortest OHO hydrogen bonds studied. Surprisingly, when the solvent polarity is low the carboxylates are protonated whereas the proton shifts toward the phenolic oxygens when the polarity is increased. This finding indicates that because of stronger ion-dipole interactions small anions are stabilized at high solvent polarity and large anions exhibiting delocalized charges at low solvent polarities. It also explains the large acidity difference of phenols and carboxylic acids in water, and the observation that this difference is strongly reduced in the interior of proteins when both partners form mutual hydrogen bonds.
The Journal of Physical Chemistry A · 47 Zitationen · DOI
Ten formally symmetric anionic OHO hydrogen bonded complexes, modeling Asp/Glu amino acid side chain interactions in nonaqueous environment (CDF(3)/CDF(2)Cl solution, 200-110 K) have been studied by (1)H, (2)H, and (13)C NMR spectroscopy, i.e. intermolecularly H-bonded homoconjugated anions of acetic, chloroacetic, dichloroacetic, trifluoroacetic, trimethylacetic, and isobutyric acids, and intramolecularly H-bonded hydrogen succinate, hydrogen rac-dimethylsuccinate, hydrogen maleate, and hydrogen phthalate. In particular, primary H/D isotope effects on the hydrogen bond proton signals as well as secondary H/D isotope effects on the (13)C signals of the carboxylic groups are reported and analyzed. We demonstrate that in most of the studied systems there is a degenerate proton tautomerism between O-H···O(-) and O(-)···H-O structures which is fast in the NMR time scale. The stronger is the proton donating ability of the acid, the shorter and more symmetric are the H-bonds in each tautomer of the homoconjugate. For the maleate and phthalate anions exhibiting intramolecular hydrogen bonds, evidence for symmetric single well potentials is obtained. We propose a correlation between H/D isotope effects on carboxylic carbon chemical shifts and the proton transfer coordinate, q(1) = ½(r(OH) - r(HO)), which allows us to estimate the desired OHO hydrogen bond geometries from the observed (13)C NMR parameters, taking into account the degenerate proton tautomerism.
The Journal of Physical Chemistry A · 45 Zitationen · DOI
The (1)H and (13)C NMR spectra of 17 OHN hydrogen-bonded complexes formed by CH(3)(13)COOH(D) with 14 substituted pyridines, 2 amines, and N-methylimidazole have been measured in the temperature region between 110 and 150 K using CDF(3)/CDF(2)Cl mixture as solvent. The slow proton and hydrogen bond exchange regime was reached, and the H/D isotope effects on the (13)C chemical shifts of the carboxyl group were measured. In combination with the analysis of the corresponding (1)H chemical shifts, it was possible to distinguish between OHN hydrogen bonds exhibiting a single proton position and those exhibiting a fast proton tautomerism between molecular and zwitterionic forms. Using H-bond correlations, we relate the H/D isotope effects on the (13)C chemical shifts of the carboxyl group with the OHN hydrogen bond geometries.
Physical Chemistry Chemical Physics · 44 Zitationen · DOI
We study a series of intermolecular hydrogen-bonded 1 : 1 complexes formed by chloroacetic acid with 19 substituted pyridines and one aliphatic amine dissolved in CD<sub>2</sub>Cl<sub>2</sub> at low temperature by <sup>1</sup>H and <sup>13</sup>C NMR and FTIR spectroscopy. The hydrogen bond geometries in these complexes vary from molecular (O-HN) to zwitterionic (O<sup>-</sup>H-N<sup>+</sup>) ones, while NMR spectra show the formation of short strong hydrogen bonds in intermediate cases. Analysis of C[double bond, length as m-dash]O stretching and asymmetric CO<sub>2</sub><sup>-</sup> stretching bands in FTIR spectra reveal the presence of proton tautomerism. On the basis of these data, we construct the overall proton transfer pathway. In addition to that, we also study by use of ab initio molecular dynamics the complex formed by chloroacetic acid with 2-methylpyridine, surrounded by 71 CD<sub>2</sub>Cl<sub>2</sub> molecules, revealing a dual-maximum distribution of hydrogen bond geometries in solution. The analysis of the calculated trajectory shows that the proton jumps between molecular and zwitterionic forms are indeed driven by dipole-dipole solvent-solute interactions, but the primary cause of the jumps is the formation/breaking of weak CHO bonds from solvent molecules to oxygen atoms of the carboxylate group.
Physical Chemistry Chemical Physics · 33 Zitationen · DOI
We present a joint experimental and quantum chemical study on the influence of solvent dynamics on the protonation equilibrium in a strongly hydrogen bonded phenol-acetate complex in CD2Cl2. Particular attention is given to the correlation of the proton position distribution with the internal conformation of the complex itself and with fluctuations of the aprotic solvent. Specifically, we have focused on a complex formed by 4-nitrophenol and tetraalkylammonium-acetate in CD2Cl2. Experimentally we have used combined low-temperature (1)H and (13)C NMR and UV-vis spectroscopy and showed that a very strong OHO hydrogen bond is formed with proton tautomerism (PhOH···(-)OAc and PhO(-)···HOAc forms, both strongly hydrogen bonded). Computationally, we have employed ab initio molecular dynamics (70 and 71 solvent molecules, with and without the presence of a counter-cation, respectively). We demonstrate that the relative motion of the counter-cation and the "free" carbonyl group of the acid plays the major role in the OHO bond geometry and causes proton "jumps", i.e. interconversion of PhOH···(-)OAc and PhO(-)···HOAc tautomers. Weak H-bonds between CH(CD) groups of the solvent and the oxygen atom of carbonyl stabilize the PhOH···(-)OAc type of structures. Breaking of CH···O bonds shifts the equilibrium towards PhO(-)···HOAc form.
The Journal of Physical Chemistry A · 33 Zitationen · DOI
The N-H stretching vibrations of adenine, one of the building blocks of DNA, are studied by combining infrared absorption and nonlinear two-dimensional infrared spectroscopy with ab initio calculations. We determine diagonal and off-diagonal anharmonicities of N-H stretching vibrations in chemically modified adenosine monomer dissolved in chloroform. For the single-quantum excitation manifold, the normal mode picture with symmetric and asymmetric NH(2) stretching vibrations is fully appropriate. For the two-quantum excitation manifold, however, the interplay between intermode coupling and frequency shifts due to a large diagonal anharmonicity leads to a situation where strong mixing does not occur. We compare our findings with previously reported values obtained on overtone spectroscopy of coupled hydrogen stretching oscillators.
The Journal of Physical Chemistry A · 27 Zitationen · DOI
To assess the potential use of O-H stretching modes of aromatic alcohols as ultrafast local probes of transient structures and photoacidity, we analyze the response of the O-H stretching mode in the 2-naphthol-acetonitrile (2N-CH3CN) 1:1 complex after UV photoexcitation. We combine femtosecond UV-infrared pump-probe spectroscopy and a theoretical treatment of vibrational solvatochromic effects based on the Pullin perturbative approach, parametrized at the density functional theory (DFT) level. We analyze the effect of hydrogen bonding on the vibrational properties of the photoacid-base complex in the S0 state, as compared to O-H stretching vibrations in a wide range of substituted phenols and naphthols covering the 3000-3650 cm(-1) frequency range. Ground state vibrational properties of these phenols and naphthols with various substituent functional groups are analyzed in solvents of different polarity and compared to the vibrational frequency shift of 2N induced by UV photoexcitation to the (1)Lb electronic excited state. We find that the O-H stretching frequency shifts follow a linear relationship with the solvent polarity function F0 = (2ε0 - 2)/(2ε0 + 1), where ε0 is the static dielectric constant of the solvent. These changes are directly correlated with photoacidity trends determined by reported pKa values and with structural changes in the O···N and O-H hydrogen-bond distances induced by solvation or photoexcitation of the hydrogen-bonded complexes.
Chemistry - A European Journal · 19 Zitationen · DOI
Aiming to extend the scope of indigoid photoswitches to polar protic environments, we have synthesized a sulfonated thioindigo derivative highly soluble in water. Studies by UV/Vis absorption, fluorescence, and NMR spectroscopy indicate that, despite aggregation effects at micromolar concentrations, the novel dye offers satisfactory performance in aqueous solution in the absence of solvation aides. Enrichment of the metastable cis isomer by irradiation may exceed 65 % and its half-life at room temperature may exceed several hours. Degradation after 20 yellow and blue light irradiation cycles within 2 hours is less than 2 %. Performance can be expected to further improve in future molecular designs if the tendency towards self-association is further reduced. Crucially, photoisomerization of indigoids is not necessarily inhibited by water and, thus, the superior spatial control offered by this class of molecular switches may be of great benefit also in biological systems.
The Journal of Physical Chemistry A · 17 Zitationen · DOI
We present a (1)H, (2)H, and (13)C NMR study of the monoanions of succinic (1), meso- and rac-dimethylsuccinic (2, 3), and methylsuccinic (4) acids (with tetraalkylammonium as the counterion) dissolved in CDF(3)/CDF(2)Cl at 300-120 K. In all four monoanions, the carboxylic groups are linked by a short intramolecular OHO hydrogen bond revealed by the bridging-proton chemical shift of about 20 ppm. We show that the flexibility of the carbon skeleton allows for two gauche isomers in monoanions 1, 2, and 4, interconverting through experimental energy barriers of 10-15 kcal/mol (the process itself and the energy barrier are also reproduced in MP2/6-311++G** calculations). In 3, one of the gauche forms is absent because of the steric repulsion of the methyl groups. In all four monoanions, the bridging proton is located in a double-well potential and subject, at least to some extent, to proton tautomerism, for which we estimate the two proton positions to be separated by ca. 0.2 Å. In 1 and 3, the proton potential is symmetric. In 2, slowing the conformational interconversion introduces an asymmetry to the proton potential, an effect that might be strong enough even to synchronize the proton tautomerism with the interconversion of the two gauche forms. In 4, the asymmetry of the proton potential is due to the asymmetric substitution. The intramolecular H-bond is likely to remain intact during the interconversion of the gauche forms in 1, 3, and 4, whereas the situation in 2 is less clear.
The Journal of Physical Chemistry Letters · 16 Zitationen · DOI
We explore in a combined UV–vis/NMR approach the hydrogen-bonded complexes of 2-chloro-4-nitrophenol (CNP) with acetate anion as a model for amino acid side-chain interactions. For the first time, we present two-dimensional UV–vis/NMR correlation spectra, measured simultaneously for the same sample inside of the magnet of a NMR spectrometer. Synchronous and asynchronous 2D plots allow us to monitor the formation of hydrogen-bonded complexes, assign the signals to specific species, and finally estimate the geometry of a hydrogen-bonded 1:1 heteroconjugated anion coexisting with four other anionic species formed in CD2Cl2 solution at 180 K. Combined analysis of NMR and UV–vis spectra with the help of previously published hydrogen-bond correlations shows that the hydrogen bond in the heteroconjugate is of the CNP–O–···HOOCCH3 type with r(O···O) ≈ 2.48 Å and the average bridging proton displacement from the hydrogen bond center of about 0.18 Å.
ChemPhotoChem · 10 Zitationen · DOI
Abstract We have synthesized and characterized a thioindigo photoswitch featuring phenolic residues forming an intramolecular hydrogen bond exclusively in the cis isomer. In acetone–water mixtures, wavelength‐dependent photostationary states reached their maximum and minimum values of up to 95 % and down to 11 % cis isomers at circa λ =580 and 480 nm, respectively. Within a few hours, room‐temperature thermal isomerization is negligible in neutral and mildly acidic solutions. Protic media decrease trans → cis but increase cis → trans quantum yields. In CD 3 OD solution, in which light of any wavelength absorbed triggers the latter process almost exclusively, a 19 F NMR titration is used to calculate p K a values of 7.2 ( trans ) and 5.0 ( cis ; both rescaled to water) corresponding to a change in dissociation constant of 2.2 orders of magnitude. Future derivatives featuring solubility and reversible photochromism in water may provide pH modulation of similar amplitude in a range adjustable by the choice of phenolic substituents.
The Journal of Physical Chemistry B · 9 Zitationen · DOI
Intramolecular hydrogen bonds in aprotic media were studied by combined (simultaneous) NMR and UV-vis spectroscopy. The species under investigation were anionic and featured single or coupled H-bonds between, for example, carboxylic groups and phenolic oxygen atoms (COO···H···OC)<sup>-</sup>, among phenolic oxygen atoms (CO···H···OC)<sup>-</sup>, and hydrogen bond chains between a carboxylic group and two phenolic oxygen atoms (COO···H···(OC)···H···OC)<sup>-</sup>. The last anion may be regarded as a small molecule model for the hydrogen bond system in the active site of wild-type photoactive yellow protein (PYP) while the others mimic the corresponding H-bonds in site-selective mutants. Proton positions in isolated hydrogen bonds and hydrogen bond chains were assessed by calculations for vacuum conditions and spectroscopically for the two media, CD<sub>2</sub>Cl<sub>2</sub> and the liquefied gas mixture CDClF<sub>2</sub>/CDF<sub>3</sub> at low temperatures. NMR parameters allow for the estimation of time-averaged H-bond geometries, and optical spectra give additional information about geometry distributions. Comparison of the results from the various systems revealed the effects of the formation of hydrogen bond chains and changes of medium conditions on the geometry of individual H-bonds. In particular, the proton in a hydrogen bond to a carboxylic group shifts from the phenolic oxygen atom in the system COO<sup>-</sup>···H-OC to the carboxylic group in COO-H···(OC)<sup>-</sup>···H-OC as a result of hydrogen bond formation to the additional phenolic donor. Increase in medium polarity may, however, induce the conversion of a structure of a type COO-H···(OC)<sup>-</sup>···H-OC to the type COO<sup>-</sup>···H-(OC)···H-OC. Application of these results obtained from the model systems to PYP suggests that both cooperative effects within the hydrogen bond chain and a low-polarity protein environment are prerequisites for the stabilization of negative charge on the cofactor and hence for the spectral tuning of the photoreceptor.
Angewandte Chemie · 9 Zitationen · DOI
Ein neuer Probenkopf für die simultane Messung von NMR- und UV/Vis-Spektren wurde entwickelt. 1H-NMR- und UV/Vis-Spektren des gezeigten Komplexes wurden in CD2Cl2 bei 175 K gemessen. Mithilfe der 1H-NMR-Spektren war es möglich, die Probenzusammensetzung so einzustellen, dass das Phenol ausschließlich als Teil des gewünschten Komplexes vorlag. Die UV/Vis-Spektren ermöglichten eine ungefähre Bestimmung der Position des Brückenprotons.
ChemPhotoChem · 8 Zitationen · DOI
Abstract The N , N ′‐di‐ tert ‐butoxycarbonylindigo parent compound and four symmetrically substituted derivatives alternatively containing methoxy and nitro substituents in positions 5 and 6 were synthesized. The photochromic behavior was studied in solvents ranging in polarity from toluene to acetonitrile/water mixtures and characterized in terms of trans and cis isomer spectra, conversion quantum yields and thermal half‐lives of the metastable cis isomers. The half‐lives at 21 °C varied from a few seconds (5‐nitro in polar solvents) to several days (6‐methoxy in apolar media) and can be described by the substituents’ Hammett constants. Spectroscopic and photochemical parameters, in contrast, are governed largely by the substituents’ resonance effects according to a scheme well known from thioindigos and these are termed here favorable and unfavorable resonance effects (FRE and URE, respectively). The title photoswitches show little propensity to quenching by protons and may be operated in aqueous media.
Physical Chemistry Chemical Physics · 8 Zitationen · DOI
A series of strong H-bonded complexes of trimethylglycine, also known as betaine, with acetic, chloroacetic, dichloroacetic, trifluoroacetic and hydrofluoric acids as well as the homo-conjugated cation of betaine with trifluoroacetate as the counteranion were investigated by low-temperature (120-160 K) liquid-state NMR spectroscopy using CDF(3)/CDF(2)Cl mixture as the solvent. The temperature dependencies of (1)H NMR chemical shifts are analyzed in terms of the solvent-solute interactions. The experimental data are explained assuming the combined action of two main effects. Firstly, the solvent ordering around the negatively charged OHX region of the complex (X = O, F) at low temperatures, which leads to a contraction and symmetrisation of the H-bond; this effect dominates for the homo-conjugated cation of betaine. Secondly, at low temperatures structures with a larger dipole moment are preferentially stabilized, an effect which dominates for the neutral betaine-acid complexes. The way this second contribution affects the H-bond geometry seems to depend on the proton position. For the Be(+)COO(-)···HOOCCH(3) complex (Be = (CH(3))(3)NCH(2)-) the proton displaces towards the hydrogen bond center (H-bond symmetrisation, O···O contraction). In contrast, for the Be(+)COOH···(-)OOCCF(3) complex the proton shifts further away from the center, closer to the betaine moiety (H-bond asymmetrisation, O···O elongation). Hydrogen bond geometries and their changes upon lowering the temperature were estimated using previously published H-bond correlations.
Angewandte Chemie · 6 Zitationen · DOI
Molekularer Autoklav: In molekularen Kapseln eingeschlossene Carbonsäure-Dimere unterliegen einem Binnendruck von 5–10 kbar, der zu einer Verkürzung der Wasserstoffbrücken führt (siehe Schema). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
Zeitschrift für Physikalische Chemie · 3 Zitationen · DOI
Abstract Associates of 3 ' ,5 ' -O-TBDMS protected derivatives of the 2 ' -deoxy forms of the nucleosides adenosine, 6-N-methyl-adenosine and thymidine (henceforward simply addressed by their parents' names) and further model systems in dichloromethane and Freon (CDClF 2 /CDF 3 ) solutions are studied at low temperatures by 1 H NMR and FT-IR spectroscopy. N⋯N distances in hydrogen bonds are estimated from chemical shifts of protons in hydrogen bonds employing geometric and spectroscopic hydrogen bond correlations. These distances are in turn employed to derive N–H stretching frequencies from IR spectroscopic hydrogen bond correlations which may be compared to corresponding experimental results. Three isomeric hydrogen bonded dimers of thymidine are characterized in Freon solution at 120 K. Binary associates of thymidine and a series of pyridines are studied; estimated N⋯N distances in the range of 3.08 to 2.85 Å are qualitatively correlated to shifts of N–H stretching bands where in all cases considerable contributions are found in the spectral region below 3000 cm -1 . For adenosine, three isomeric binary associates with 4-nitrophenol are found allowing for an assessment of site-specific acceptor capabilities. In associates of thymidine and adenosine, Watson-Crick and Hoogsteen type 1:1 associates (estimated N⋯N distances of 2.85 and 2.90 Å) as well as 2:1 associates bearing only marginally longer H-bonds could be characterized. Two 1:1 associates between thymidine and 6-N-methyl-adenosine are described that are exclusively bonded via N–H⋯N bridges of about 2.97 and 3.08 Å for Watson-Crick and Hoogsteen sites, respectively, which leads to the conclusion that cooperative effects among coupled N–H⋯O and N–H⋯N hydrogen bonds in A-T base pairs are significant as formation of the N–H⋯O bond induces a contraction of around 0.15 Å in the neighboring N–H⋯N bond.
Journal of Labelled Compounds and Radiopharmaceuticals · 1 Zitationen · DOI
A variation of the Perkin reaction using a nonenolizable anhydride as the condensation agent allows for the effective conversion of valuable carboxylic acids to the corresponding cinnamates.
EPJ Web of Conferences · 1 Zitationen · DOI
We characterize diagonal and off-diagonal anharmonicities of N-H stretching vibrations in adenosine and thymidine monomers and in A•T-base pairs in chloroform solution, showing the important role of coupling between vibrationally excited N-H stretching states.
Physical Chemistry Chemical Physics
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- Dr. Benjamin Koeppe
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- Mathematisch-Naturwissenschaftliche Fakultät
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- Institut für Chemie
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- Organische Chemie und Funktionale Materialien
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