One- and two-dimensional C–H/N–H dipolar correlation experiments under fast magic-angle spinning for determining the peptide dihedral angle φ

A recently proposed ¹³C–¹H recoupling sequence operative under fast magic-angle spinning (MAS) [K. Takegoshi, T. Terao, Solid State Nucl. Magn. Reson. 13 (1999) 203–212.] is applied to observe ¹³C–¹H and ¹⁵N–¹H dipolar powder patterns in the ¹H–¹⁵N–¹³C–¹H system of a peptide bond. Both patterns are correlated by ¹⁵N-to-¹³C cross polarization to observe one- or two-dimensional (1D or 2D) correlation spectra, which can be simulated by using a simple analytical expression to determine the H–N–C–H dihedral angle. The 1D and 2D experiments were applied to N-acetyl[1,2-¹³C,¹⁵N] -valine, and the peptide φ angle was determined with high precision by the 2D experiment to be ±155.0°±1.2°. The positive one is in good agreement with the X-ray value of 154°±5°. The 1D experiment provided the value of φ=±156.0°±0.8°.     

Measurement of one and two bond N–C couplings in large proteins by TROSY-based J-modulation experiments

Residual dipolar couplings (RDCs) between NC′ and NC^α atoms in polypeptide backbones of proteins contain information on the orientation of bond vectors that is complementary to that contained in NH RDCs. The ¹J_NC^α and ²J_NC^α scalar couplings between these atoms also display a Karplus relation with the backbone torsion angles and report on secondary structure. However, these N–C couplings tend to be small and they are frequently unresolvable in frequency domain spectra having the broad lines characteristic of large proteins. Here a TROSY-based J-modulated approach for the measurement of small ¹⁵N–¹³C couplings in large proteins is described. The cross-correlation interference effects inherent in TROSY methods improve resolution and signal to noise ratios for large proteins, and the use of J-modulation to encode couplings eliminates the need to remove frequency distortions from overlapping peaks during data analysis. The utility of the method is demonstrated by measurement of ¹J_NC′, ¹J_NC^α, and ²J_NC^α scalar couplings and ¹D_NC′ and ¹D_NC^α residual dipolar couplings for the myristoylated yeast ARF1·GTPγs protein bound to small lipid bicelles, a system with an effective molecule weight of 70 kDa.     

Magnitudes and Orientations of the N Chemical Shift Tensor of [1-N]-2′-Deoxyguanosine Determined on a Polycrystalline Sample by Two-Dimensional Solid-State NMR Spectroscopy

The magnitudes and orientations of the ¹⁵N chemical shift tensor of [1-¹⁵N]-2′-deoxyguanosine were determined from a polycrystalline sample using the two-dimensional PISEMA experiment. The magnitudes of the principal values of the ¹⁵N chemical shift tensor of the N1 nitrogen of [1-¹⁵N]-2′-deoxyguanosine were found to be ς₁₁ = 54 ppm, ς₂₂ = 148 ppm, and ς₃₃ = 201 ppm with respect to (¹⁵NH₄)₂SO₄ in aqueous solution. Comparisons of experimental and simulated two-dimensional powder pattern spectra show that ς_33N is approximately collinear with the N–H bond. The tensor orientation of ς_33N for N1 of [1-¹⁵N]-2′-deoxyguanosine is similar to the values obtained for the side chain residues of ¹⁵N_ε1-tryptophan and ¹⁵N_π-histidine even though the magnitudes differ significantly.     

Status of the INR experiment on 2β decay of Cd

Measurements of ¹¹⁶Cd double beta decay with help of enriched¹¹⁶CdWO₄ crystal scintillator are in progress in the Solotvina Underground Laboratory. The last part of the exposition with the background rate less than 0.6 counts/y·kg·keV (in the region of interest 2.7–2.9 MeV) is about 19000 hours. The half-life limit T1/2(0ν)≥3.2·10²² y (90% C.L.) is obtained for neutrinoless 2β decay of ¹¹⁶Cd. It corresponds to restrictions on the values of the neutrino mass m_ν≤3.9 eV, right-handed admixtures in weak interaction η≤5.7·10⁻⁸, λ5.0·10⁻⁶ and R-parity violating parameter of minimal supersymmetric standard model ≤1.1·10⁻³. For neutrinoless modes with emission of one and two Majorons, the limits T1/2(0νM1)≥1.2·10²¹ y and T1/2(0νM2)≥2.4·10²⁰ y (90% C.L.) are determined. To advance these results to a level of the limit m_ν≤1–2 eV, the improved set-up with four enriched ¹¹⁶CdWO₄ crystals is in mounting low.     

Isoscalar quadrupole strength in Ca from the (p,p′α0) reaction at Ep = 100 MeV

The ⁴⁰Ca(p,p′ α) reaction has been studied at an incident proton energy E_p = 99.5 MeV for proton laboratory scattering angles Θ_p^lab = 17°, 23° and 27°. Emission of α particles coincident with the scattered proton has been measured for an angular range Θ_α 0° − 180° relative to the recoil axis. A multipole decomposition for the α₀-decay channel to the ³⁶Ar ground state has been performed from the angular-correlation functions. The energy distribution of the dominating E2 strength deduced in the excitation energy range E_x = 11–21 MeV agrees reasonably well with the results from electron and α-induced α₀-decay investigations. The exhaustion of the E2 energy-weighted sum rule in this channel up to an energy of 17 MeV is 16.1(4.0)%, in accord with the study of the (α, α′ α₀) reaction. However, this value is twice what is found in the (e,e′ α₀) experiment in the same energy region. Thus, the puzzling discrepancy in the E2 strengths derived from electromagnetic and hadronic probes remains unsolved.     

The Fe(α, γ)Ni reaction at excitation energies in the region of the giant dipole resonance

Excitation functions for the ⁵⁶Fe(α, γ₀)⁶⁰Ni and ⁵⁶Fe(α, γ₁)⁶⁰Ni reactions have been measured at 90° to the beam direction over the bombarding energy range 8.0–17.6 MeV. Gamma-ray angular distributions were measured at ten bombarding energies. Excitation functions for the ⁵⁹Co(p, γ₀)⁶⁰Ni and ⁵⁹Co(p, γ₁)⁶⁰Ni reactions were measured over the range E_x = 16.58–16.92 MeV and compared with the (α, γ) data. The angular distribution data indicate that the (α, γ₀) and (α,γ₁) reactions proceed through 1⁻, and 1⁻ and 3⁻ states, respectively. The (α, γ) excitation functions are discussed with respect to isospin splitting of the ⁶⁰Ni giant dipole resonance. The fine structure observed in the excitation functions is shown to be most probably due to Ericson fluctuations. The gross (α, γ) cross sections are shown to be in reasonable agreement with the results of calculations made using the theory of Hauser and Feshbach assuming excitation of the giant dipole resonance.     

Flavor symmetry, K– mixing and new physics effects on CP violation in D and Ds decays

Flavor symmetry and symmetry breaking, K⁰– mixing and possible effects of new physics on CP violation in weak decay modes D^±→K_S,L+X^±, (K_S,L+π⁰)_K^*+X^± (for X=π,ρ,a₁) and D^±_s→K_S,L+X^±_s, (K_S,L+π⁰)_K^*+X^±_s (for X_s=K,K^*) are analyzed. Relations between D^± and D^±_s decay branching ratios are obtained from the ds subgroup of SU(3) and dominant symmetry-breaking mechanisms are investigated. A CP asymmetry of magnitude 3.3×10⁻³ is shown to result in the standard model from K⁰– mixing in the final-state. New physics affecting the doubly Cabibbo-suppressed channels might either cancel this asymmetry or enhance it up to the percent level. A comparison between the CP asymmetries in D^±_(s)→K_SX^±_(s) and D^±_(s)→K_LX^±_(s) can pin down effects of new physics.     

High-resolution infrared spectra of HCF3 in the ν6 (500 cm) and 2ν6 (1000 cm) regions: rovibrational analysis and accurate determination of the ground state constants C0 and DK

The high-resolution infrared spectrum of HCF₃ was studied in the ν₆ fundamental (near 500 cm⁻¹) and in the 2ν₆ overtones (near 1000 cm⁻¹) regions. The present study reports on the analysis of the hot bands in the ν₆ region, as well as the first observation and assignment of the 2ν₆² perpendicular band. Using ν₆, 2ν₆^±2–ν₆^±1 and 2ν₆² experimental wavenumbers, accurate coefficients C₀ and D_K⁰ of the K-dependent ground-state energy terms were obtained, using the so-called “loop method.” Ground-state energy differences Δ(K,J)=E₀(K,J)−E₀(K−3,J) were obtained for K=3–30. A least-squares fit of 81 such differences gave the following results (in cm⁻¹): C₀=0.1892550(15); D_K⁰=2.779(26) × 10⁻⁷.     

Lorentz-mikroskopie von Bloch- und Néelwänden in Ni-Fe-kristallen

We prepared thin single crystal foils of 50 Ni 50 Fe for observation in a 100 kV electron microscope. Due to its high saturation induction and low anisotropy, magnetic domain walls can be easily observed in this material. The effective anisotropy which governs the wall angles consists of crystal anisotropy and superimposed random stress anistropies so that wall angles of any magnitude are found.In accordance with theory three distinct wall types are identified for film thickness between 500 Å and 2000 Å as a function of wall angle θ: (i) the asymmetric Bloch wall for 180° θ #62; 140°, (ii) the asymmetric Néel wall for 140° #62; θ #62; θ_s, and (iii) the symmetric Néel wall for θ_s #62; θ, where θ_s is an angle which decreases with increasing film thickness.     

Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

C, N CPMAS NMR and GIAO DFT calculations of stereoisomeric oxindole alkaloids from Cat's Claw (Uncaria tomentosa)

Oxindole alkaloids, isolated from the bark of Uncaria tomentosa [Willd. ex Schult.] Rubiaceae, are considered to be responsible for the biological activity of this herb. Five pentacyclic and two tetracyclic alkaloids were studied by solid-state NMR and theoretical GIAO DFT methods. The ¹³C and ¹⁵N CPMAS NMR spectra were recorded for mitraphylline, isomitraphylline, pteropodine (uncarine C), isopteropodine (uncarine E), speciophylline (uncarine D), rhynchophylline and isorhynchophylline. Theoretical GIAO DFT calculations of shielding constants provide arguments for identification of asymmetric centers and proper assignment of NMR spectra. These alkaloids are 7R/7S and 20R/20S stereoisomeric pairs. Based on the ¹³C CP MAS chemical shifts the 7S alkaloids (δ C3 70–71 ppm) can be easily and conveniently distinguished from 7R (δC3 74.5–74.9 ppm), also 20R (δC20 41.3–41.7 ppm) from the 20S (δC20 36.3–38.3 ppm). The epiallo-type isomer (3R, 20S) of speciophylline is characterized by a larger ¹⁵N MAS chemical shift of N4 (64.6 ppm) than the allo-type (3S, 20S) of isopteropodine (δN4 53.3 ppm). ¹⁵N MAS chemical shifts of N1–H in pentacyclic alkaloids are within 131.9–140.4 ppm.     

Angular distribution measurements of Li(p,α)He reaction at 140 keV proton energy using nuclear track detectors

Angular distributions of a ⁶Li(p,α) ³He reaction were measured at six angles for 140 keV proton energy using nuclear track detectors (NTDs). The measurements were carried out over 60°–160° lab. angles in 20° increments using a scattering chamber of 80° beam line of the 350 kV accelerator. A semiconductor silicon surface barrier (SSB) detector was placed at +160° and was used as a monitor. The results have shown that the CR-39 detector has excellent capabilities to distinguish 1.4–2.7 MeV α+ ³He particles from the ⁶Li(p,α) ³He reaction and 8–9.4 MeV α-particles from the ⁷Li(p,α) ⁴He reaction through their track diameters. However, it was not possible to distinguish between the 2.3 MeV ³He ions and the 1.7 MeV ⁴He ions from the ⁶Li(p,α) ³He reaction from their track diameter measurements, but it was possible to differentiate between the two, from the darker contrast of the ³He particles caused by its deeper tracks as compared to those of ⁴He.     

Dynamic properties of P4O6S and P4O7: P spin–echo and P MAS–NMR investigations

The rotational dynamics of P₄O₆S and P₄O₇ in the solid state were studied by means of ³¹P NMR spectra of spinning and static powder samples in the temperature range of 153–295 K and 295–388 K, respectively. All spectra were simulated to confirm the type of the motion and to extract the time scales as a function of the temperature. Good agreement between experimental and theoretical data was obtained on the basis of a three-site jump model. For P₄O₆S, the activation energy and the pre-exponential factor derived from the lineshape simulations amount to 51(2) kJ/mol and 6(3)·10¹⁵ s⁻¹. For P₄O₇, the spectral analysis yields an activation energy of 67(1) kJ/mol and a pre-exponential factor of 6(2)·10¹⁴ s⁻¹. The dynamic behavior was checked independently by lineshape analyses under both MAS and static conditions. Activation energies are consistent within the errors for the lineshape analyses. Additionally, we have analyzed spin–lattice relaxation measurements, which show the correct trends for the activation energies.     

Looking for double beta decay of Nd to excited states of Sm by gamma ray spectroscopy

We have measured the gamma ray activity of a sample of 6189 grams of metallic Neodimium with a germanium detector. From the gamma energy spectrum recorded during almost 6500 hours we extract lower limits for the halflife of the inclusive (0ν + 2ν) ββ decay of ¹⁵⁰Nd to the first excited states of ¹⁵⁰Sm : t_1/2(0⁺ → 0₁⁺ > 1.0·10²⁰, t_1/2(O⁺ → 0₂⁺) > 2.0 · 10²⁾, t_1/2(0⁺ → 2₁⁺) > 9.1 · 10¹⁹.     

The (γ,p) reaction in Au

Proton energy spectra of the ¹⁹⁷Au(e,p) reaction were measured in the region between 17 and 30 MeV at three angles: 40°, 90° and 140°. Two prominent bumps were observed in the (γ,p) spectra converted using virtual photon theory. The higher-energy bump shifts with photon energies and the lower-energy one stays at 10.5 MeV. The higher-energy bump is much larger at 40° than at 140°; on the contrary the angular dependence of the lower-energy bump is small. Neither bump can be described by a statistical calculation. A calculation of a microscopic shell model shows that the lower-energy bump is attributed to the decay of proton-particle–neutron-hole pairs in the T_> states, leaving a neutron hole around the Fermi surface. The higher-energy bump can be ascribed to the direct–semidirect mechanism. This paper gives the solution to a part of the long-standing question about the origin of photo-proton emission in heavy nuclei.     

Non-Kramers ENDOR and ESEEM of the S = 2 Ferrous Ion of [Fe(II)EDTA]

We report here the first non-Kramers (NK) ESEEM and ENDOR study of a mononuclear NK center, presenting extensive parallel-mode ESEEM and ENDOR measurements on the S_t = 2 ferrous center of [Fe(II)ethylenediamine-N,N,N′,N′-tetraacetato]²⁻; [Fe(II)EDTA)]²⁻. The results disclose an anomalous equivalence of the experimental patterns produced by the two techniques. A simple theoretical treatment of the frequency-domain patterns expected for NK-ESEEM and NK-ENDOR rationalizes this correspondence and further suggests that the very observation of NK-ENDOR is the result of an unprecedentedly large hyperfine enhancement effect. The mixed nitrogen–carboxylato oxygen coordination of [Fe(II)EDTA]²⁻ models that of the protein-bound diiron centers, although with a higher coordination number. Analysis of the NK-ESEEM measurements yields the quadrupole parameters for the ¹⁴N ligands of [Fe(II)EDTA]²⁻, K = 1.16(1) MHz, 0 ≤ η ≤ 0.05, and the analysis indicates that the electronic zero-field splitting tetragonal axis lies along the N–N direction.     

The Microwave Spectrum of m-Tolunitrile: Methyl Internal Rotation and N Nuclear Quadrupole Coupling

The microwave spectrum of m-tolunitrile (3-methylbenzonitrile, m-C₆H₄CH₃CN) has been investigated in the frequency range from 1 to 4 and 8 to 26.5 GHz. The spectra in the two lowest states of internal methyl rotation (m = 0, ±1) were recorded by means of pulsed molecular beam Fourier transform microwave (MB-FTMW) spectrometers. The interpretation of the spectra was based on an asymmetric frame–symmetric top Hamiltonian with inclusion of centrifugal distortion terms and first-order contributions from ¹⁴N nuclear quadrupole coupling. A least-squares analysis yielded the rotational constants A = 3295.9103(10) MHz, B = 1199.1188(2) MHz, C = 883.9223(1) MHz, all elements of the nuclear quadrupole coupling tensor χ_aa = −3.626(1) MHz, χ_bb = 1.684(1) MHz, χ_cc = 1.943(1) MHz, and χ_ab = −1.870(3) MHz, as well as the threefold barrier to internal rotation, V₃ = 14.2 cm⁻¹, and the angle between the internal rotor axis and the principal moment of inertia a axis, θ = 42.66°, using fixed values for the sixfold barrier term V₆ (−11 cm⁻¹) and the moment of inertia of the methyl top I_α (3.16 u Ų).     

Eley–Rideal reaction dynamics between O atoms on β-cristobalite (1 0 0) surface: A new interpolated potential energy surface and classical trajectory study

We present a theoretical study of the collisions of atomic oxygen with O-precovered β-cristobalite (1 0 0) surface. We have constructed a multidimensional potential energy surface for the O₂/β-cristobalite (1 0 0) system based mainly on a dense grid of density functional theory points by using the interpolation corrugation-reducing procedure. Classical trajectories have been computed for quasithermal (100–1500 K) and state-specific (e.g., collision energies between 0.01 and 4 eV) conditions of reactants for different O incident angles (θ_v). Atomic sticking and O_2(adsorbed) formation are the main processes, although atomic reflection and Eley–Rideal (ER) reaction (i.e., O₂ gas) are also significant, depending their reaction probabilities on the O incident angle. ER reaction is enhanced by temperature increase, with an activation energy derived from the atomic recombination coefficient (γ_O(θ_v = 0°, T)) equal to 0.24 ± 0.02 eV within the 500–1500 K range, in close agreement with experimental data. Calculated γ_O(θ_v = 0°, T) values compare quite well with available experimental γ_O(T) although a more accurate calculation is proposed. Chemical energy accommodation coefficient β_O(T) is also discussed as a function of ER and other competitive contributions.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

The microwave spectrum of 1-phosphabut-3-ene-1-yne, CH2=CHCP

The new molecule 1-phosphabut-3-ene-1-yne, CH₂=CHCP, produced by pyrolyzing prop-1-ene-3-phosphorus dichloride, CH₂=CHCH₂PCl₂, was detected by microwave spectroscopy. The analysis of the rotational transitions indicates that the molecule is planar with constants: A₀ = 46 694(24), B₀ = 2807.7100(21), and C₀ = 2645.8356(21) MHz. These rotational constants indicate that the structure of the vinyl group is essentially the same as that in CH₂=CHCN and CH₂=CHCCH; r(C---C) = 1.432 Å and (C=C---C) = 123.9°. The dipole moment parameters are μ_A = 1.181(2), μ_B = 0.074(1), and μ = 1.183(2) D. The vibrational satellite spectra for the C---CP bending modes indicate that ν₁₁(a′) = 184 ± 30 cm⁻¹ and ν₁₅(a″) = 263 ± 30 cm⁻¹.