On the Macrolactonization of β-Hydroxy Acids. Crystal structures of the pentolide and the hexolide from (R)-3-hydroxybutanoic acid. Molecular modeling studies of the tetrolide

The temperature and concentration dependence of the previously reported formation of oligolides from (R)- or (S)-3-hydroxybutanoic acid under Yamaguchi's macrolactonization conditions (2,4,6-trichlorobenzoyl chloride/base) was studied. While the content of hexolide 2 in the product mixture is almost invariably ca. 35%, the amounts of pentolide 1 and of the larger rings strongly depend upon the temperature employed (Fig.1). Cyclic oligomers ( 5,6 ) are also obtained from 3-hydroxypentanoic acid. Enantiomerically pure β-butyrolactone can be used for the preparation of pento-, hexo-, and heptolide under Shanzer's macrolactonization conditions (tetra-oxadistannacyclodecane ‘template’). The X-ray crystal structures of the pentolide 1 and of two modifications (space groups C 2 and P 2₁) of the hexolide 2 were determined (Figs. 2–6 and Tables 1 and 5). No close contacts between substituent atoms and atoms in the rings or between ring atoms are observed in these structures. The hexolide C 2 modification is ‘just a large ring’, while the crystals of the P 2₁ modification contain folded rings the backbones of which resemble the seam of a tennis ball. A comparison of the torsion angles in the folded hexolide ring of the P 2₁ modification with those in the helical poly-(R)-3-hydroxybutanoate ( PHB ) suggests (Table 2) that the same interactions might be responsible for folding in the first and helix formation in the second case. Molecular modeling with force-field energy minimization of the tetrolide from four homochiral β-hydroxybutanoic acid units was undertaken, in order to find possible reasons for the fact that we failed to detect the tetrolide in the reaction mixtures. The calculated conformational energies (per monomer) for some of the tetrolide models (Figs. 7–9 and Tables 3 and 4) are not significantly higher than for the pentolide and hexolide crystal structures. We conclude that thermodynamic instability is an unlikely reason for the lack of tetrolide isolation. This result and failure to observe equilibration of pentolide 1 to a mixture of oligomers under the reaction conditions suggest that product distribution is governed by kinetic control.     

High resolution NMR study of T1 magnetic relaxation dispersion. II. Influence of spin-spin couplings on the longitudinal spin relaxation dispersion in multispin systems

Effects of scalar spin-spin interactions on the nuclear magnetic relaxation dispersion (NMRD) of coupled multispin systems were analyzed. Taking spin systems of increasing complexity we demonstrated pronounced influence of the intramolecular spin-spin couplings on the NMRD of protons. First, at low magnetic fields where there is strong coupling of spins the apparent relaxation times of the coupled spins become equal. Second, there are new features, which appear at the positions of the nuclear spin level anticrossings. Finally, in coupled spin systems there can be a coherent contribution to the relaxation kinetics present at low magnetic fields. All these peculiarities caused by spin-spin interactions are superimposed on the features in NMRD, which are conditioned by changes of the motional regime. Neglecting the effects of couplings may lead to misinterpretation of the NMRD curves and significant errors in determining the correlation times of molecular motion. Experimental results presented are in good agreement with theoretical calculations.     

High resolution field desorption mass spectrometry

Summary The first complete mass spectra of unprotected dinucleotides e.g. TpT, GpU, ApC, and CpA are reported. In all cases these spectra make possible the determination of the molecular weight. In addition structural information about the building blocks of the dinucleotides can be obtained.

---

Hochauflösungs-Felddesorptions-MassenspektrometrieIV. Dinucleotide

Zusammenfassung Die ersten vollständigen Massenspektren von underivatisierten Dinucleotiden wie TpT, GpU, ApC und CpA werden beschrieben. In allen Fällen ermöglicht die Felddesorptions-Massenspektrometrie die Bestimmung des Molekulargewichtes. Zusätzlich liefert die Methode wichtige Strukturinformation über die Bausteine der Dinucleotide.

---

Abbreviations MS mass spectrometry, mass spectrum - TMS trimethylsilyl - FD field desorption - M molecular ion - HR high resolution - e.h.c. emitter heating current - BAT best anode temperature Part III: Schulten, H.-R., Kümmler, D.: Sulphonic acids and sulphonates. Z. Anal. Chem.278, 13 (1976).     

BLUE LIGHT INDUCED, REVERSIBLE IN ACTIVATION OF THE TONOPLAST-TYPE H+-ATPase FROM CORN COLEOPTILES IN THE PRESENCE OF FLAVINS

Abstract— Irradiation (λ_max 447 nm; 58.5 W m^-2) of a microsomal membrane fraction of corn coleoptiles for 5 min in the presence of the in vivo concentration of riboflavin inactivates the tonoplast-type H⁺-ATPase. This inhibition is O₂-dependent, is enhanced in D₂O and suppressed by NaN₃, indicating participation of singlet molecular oxygen in the inactivating mechanism. Besides singlet oxygen, the superoxide anion (O₂^-) is generated during irradiation, which obviously has no effect on the H⁺-pumping activity. However, in the presence of superoxide dismutase (SOD), O₂^- is transformed into H₂O₂ which causes an additional strong inhibition of H⁺. ATPase activity. This inhibition can be increased by ethylenediaminetetraacetic acid (EDTA), which is known to be an electron donor of the excited flavin molecule. In contrast, catalase prevents the H₂O₂-mediated photoinactivation of the H⁺ -ATPase. The light dependent inactivation of H⁺-transport does not occur if reduced glutathion (GSH) is added prior to or after irradiation. These results indicate that the blue light mediated inhibition of the H⁺-ATPase is mediated by singlet oxygen and H₂O₂ which oxidize essential SH-groups of the enzyme into disulfides. Reduction of the formed disulfides by GSH restores the activity of the enzyme.     

S0 and S1 state structure, methyl torsional barrier heights, and fast intersystem crossing dynamics of 5-methyl-2-hydroxypyrimidine

We report the analysis of the S1<--S0 rotational band contours of jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. Unlike thymine, which exhibits a structureless spectrum, the vibronic spectrum of 5M2HP is well structured, allowing us to determine the rotational constants and the methyl group torsional barriers in the S0 and S1 states. The 0(0)(0), 6a(0)(1), 6b(0)(1), and 14(0)(1) band contours were measured at 900 MHz (0.03 cm(-1)) resolution using mass-specific two-color resonant two-photon ionization (2C-R2PI) spectroscopy. All four bands are polarized perpendicular to the pyrimidine plane (>90% c type), identifying the S1<--S0 excitation of 5M2HP as a 1nπ* transition. All contours exhibit two methyl rotor subbands that arise from the lowest 5-methyl torsional states 0A" and 1E". The S0 and S1 state torsional barriers were extracted from fits to the torsional subbands. The 3-fold barriers are V3" = 13 cm(-1) and V3' = 51 cm(-1); the 6-fold barrier contributions V6" and V6' are in the range of 2-3 cm(-1) and are positive in both states. The changes of A, B, and C rotational constants upon S1 <--S0 excitation were extracted from the contours and reflect an “anti-quinoidal” distortion. The 0(0)(0) contour can only be simulated if a 3 GHz Lorentzian line shape is included, which implies that the S1(1nπ*) lifetime is ~55 ps. For the 6a(0)(1) and 6b(0)(1) bands, the Lorentzian component increases to 5.5 GHz, reflecting a lifetime decrease to ~30 ps. The short lifetimes are consistent with the absence of fluorescence from the 1nπ* state. Combining these measurements with the previous observation of efficient intersystem crossing (ISC) from the S1 state to a long-lived T1 (3nπ*) state that lies ~2200 cm(-1) below [S. Lobsiger, S. et al. Phys. Chem. Chem. Phys. 2010, 12, 5032] implies that the broadening arises from fast intersystem crossing with k(ISC) ≈ 2 × 10(10) s(-1). In comparison to 5-methylpyrimidine, the ISC rate is enhanced by at least 10 000 by the additional hydroxy group in position 2.     

Theory of the Overhauser effect in the pulsed mode of EPR pumping: exploiting the advantages of coherent electron spin motion

A theoretical approach is proposed to describe Overhauser-type Dynamic Nuclear Polarization (DNP) for pulsed EPR pumping by application of a train of short pulses with a duration on the nanosecond time scale. We obtained an elegant general expression for the NMR enhancement provided by the DNP effect. The expression for the enhancement is similar to that known for cw-pumping except for the saturation factor, which is re-defined as the deviation of the electron spin magnetization from its equilibrium value averaged over the cycle of the pulse sequence. It is shown that one can achieve the maximal theoretically allowed NMR enhancement for pulsed pumping even when the duty cycle of pumping is low. This becomes possible because coherent motion of the electron spins in the B(1)-field is exploited, a key feature of the pulsed DNP experiment also enabling optimization of the achievable NMR enhancement. The dependence of the effect on the duty cycle, pulse duration and electron spin relaxation times has been studied in detail. Once the lines in the EPR spectrum are inhomogeneously broadened, higher DNP effects are expected in the pulsed pumping mode than in the cw-mode for the same total power of microwave irradiation. The theoretical results are in good agreement with experimental data obtained for the pumping frequencies of 300 MHz and 1.4 GHz.     

Comparison of inner-shell ionization by relativistic electron and positron impact

Ratios of K/L shell X-ray yields by 10–20 MeV electrin and positron impact on Au have been measured with an accuracy of better than ±1.6%. The results show that the K-shell X-ray production cross section by electron impact is about 2% larger than by positron impact.