Cooling overall spin temperature: protein NMR experiments optimized for longitudinal relaxation effects

In experiments performed on protonated proteins at high fields, 80% of the NMR spectrometer time is spent waiting for the ¹H atoms to recover their polarization after recording the free induction decay. Selective excitation of a fraction of the protons in a large molecule has previously been shown to lead to faster longitudinal relaxation for the selected protons [K. Pervushin, B. Vögeli, A. Eletsky, Longitudinal ¹H relaxation optimization in TROSY NMR spectroscopy, J. Am. Chem. Soc. 124 (2002) 12898–12902; P. Schanda, B. Brutscher, Very fast two-dimensional NMR spectroscopy for real-time investigation of dynamic events in proteins on the time scale of seconds, J. Am. Chem. Soc. 127 (2005) 8014–8015; H.S. Attreya, T. Szyperski, G-matrix Fourier transform NMR spectroscopy for complete protein resonance assignment, Proc. Natl. Acad. Sci. USA 101 (2004) 9642–9647]. The pool of non-selected protons acts as a “thermal bath” and spin-diffusion processes (“flip-flop” transitions) channel the excess energy from the excited pool to the non-selected protons in regions of the molecule where other relaxation processes can dissipate the excess energy. We present here a sensitivity enhanced HSQC sequence (COST-HSQC), based on one selective E-BURP pulse, which can be used on protonated ¹⁵N enriched proteins (with or without ¹³C isotopic enrichment). This experiment is compared to a gradient sensitivity enhanced HSQC with a water flip-back pulse (the water flip-back pulse quenches the spin diffusion between ¹H^N and ¹H^α spins). This experiment is shown to have significant advantages in some circumstances. Some observed limitations, namely sample overheating with short recovery delays and complex longitudinal relaxation behaviour are discussed and analysed.     

A particular solution of Heun equation for Hulthen and Woods‐Saxon potentials

In this article a particular solution of Heun equation is derived by making use of the Nikiforov‐Uvarov (NU) method which provides exact solutions for general hypergeometric equation and eigenvalues together with eigenfunctions of the Heun equation for this particular solution are obtained. One to one correspondence (isomorphism) of the aforesaid equation with the radial Schrödinger equation is emphasized and also physical counterparts of the parameters in this equation are put forward by introducing solutions for two different potential functions (Hulthen and Woods‐Saxon potentials).

     

Adsorption of cyclic hydrocarbons on Pt and the interaction of the adsorbed species with hydrogen

The adsorption of six-membered hydrocarbon cycles and cyclopentane and the interaction of hydrogen with the adsorbed layer on polycrystalline Pt-foil have been studied. The work function change (Δφ) was followed by a Kelvin probe and the C/Pt peak ratio was determined by Auger electron spectroscopy. Combining these two techniques made it possible to distinguish between chemisorption via σ-bonds and π-complex formation. Benzene and toluene adsorbed first as π-complex while cyclohexane showed initially a partial aromatization and a π-complex-like bonding to the surface. Excess hydrocarbon or addition of hydrogen transformed the π-complex into σ-bonded species. Cyclopentane adsorbed via σ-bonds and showed no significant hydrogen effect.     

Electron delocalization and dimerization in solid C59N doped C60 fullerene

Electron spin resonance and ab initio electronic structure calculations show an intricate relation between molecular rotation and chemical bonding in the dilute solid solution. The unpaired electron of C59N is delocalized over several C60 molecules above 700 K, while at lower temperatures it remains localized within short range. The data suggest that below 350 K rigid C59N-C60 heterodimers are formed in thermodynamic equilibrium with dissociated rotating molecules. The structural fluctuations between heterodimers and dissociated molecules are accompanied by simultaneous electron spin transfer between C60 and C59N molecules. The calculation confirms that in the C59N-C60 heterodimer the spin density resides mostly on the C60 moiety, while it is almost entirely on C59N in the dissociated case.     

Ab initio potential energy surface and pressure broadening coefficients for the He-CH3F complex

Symmetry-adapted perturbation theory has been applied to compute the He-CH₃F potential with the CH₃F molecule assumed rigid. The potential has a global minimum of −48.9 cm⁻¹ at the center of mass separation of 7.2 bohr with the helium atom lying along the C-F bond on the hydrogen’s side. The computed points were fitted to an analytic energy surface with a correct asymptotic behaviour. This potential has been used to compute the pressure broadening (PB) coefficients for the (j, k) = (0, 0) → (1, 0) and (1, 0) → (2, 0) rotational transitions of CH₃F perturbed by helium for a wide range of temperatures. Close-coupling results are compared with the experimental data of Willey et al. [J. Chem. Phys. 97 (1992) 4723], Beaky et al. [J. Mol. Struct. 352/353 (1995) 245] and infinite order sudden results are compared with those of Grigoriev et al. [J. Mol. Struct. 186 (1997) 48] for the ν₆ band of CH₃F perturbed by helium at room temperature. To our knowledge, present work is the first attempt of making fully ab initio calculations of collisional cross-sections and pressure broadening coefficients for this simple symmetric top system at low and room temperature.     

Effect of temperature on the synthesis of silver nanoparticles with polyethylene glycol: new insights into the reduction mechanism

Polyethylene glycol (PEG) molecules act as a reducing and stabilizing agent in the formation of silver nanoparticles. PEG undergoes thermal oxidative degradation at temperatures over 70 °C in the presence of oxygen. Here, we studied how the temperature and an oxidizing atmosphere could affect the synthesis of silver nanoparticles with PEG. We tested different AgNO₃ concentrations for nanoparticles syntheses using PEG of low molecular weight, at 60 and 100 °C. At the higher temperature, the reducing action of PEG increased and the effect of PEG/Ag⁺ ratio on nanoparticles aggregation changed. These results suggest that different synthesis mechanisms operate at 60 and 100 °C. Thus, at 60 °C the reduction of silver ions can occur through the oxidation of the hydroxyl groups of PEG, as has been previously reported. We propose that the thermal oxidative degradation of PEG at 100 °C increases the number of both, functional groups and molecules that can reduce silver ions and stabilize silver nanoparticles. This degradation process could explain the enhancement of PEG reducing action observed by other authors when they increase the reaction temperature or use a PEG of higher molecular weight     

Field sources in a Lorentz-symmetry breaking scenario with a single background vector

The present work is a generalization of the recent work [arXiv.1206.1420] on the modified Hawking temperature on the event horizon. Here the Hawking temperature is generalized by multiplying the modified Hawking temperature by a variable parameter \(\alpha \) representing the ratio of the growth rate of the apparent horizon to that of event horizon. It is found that both the first and the generalized second law of thermodynamics are valid on the event horizon for any fluid distribution. Subsequently, the Bekenstein entropy is modified on the event horizon and the thermodynamical laws are examined. Finally, an interpretation of the parameters involved is presented.     

Ion–laser interactions: The most complete solution

Trapped ions are considered one of the best candidates to perform quantum information processing. By interacting them with laser beams they are, somehow, easy to manipulate, which makes them an excellent choice for the production of nonclassical states of their vibrational motion, the reconstruction of quasiprobability distribution functions, the production of quantum gates, etc. However, most of these effects have been produced in the so-called low intensity regime, this is, when the Rabi frequency (laser intensity) is much smaller than the trap frequency. Because of the possibility to produce faster quantum gates in other regimes it is of importance to study this system in a more complete manner, which is the motivation for this contribution. We start by studying the way ions are trapped in Paul traps and review the basic mechanisms of trapping. Then we show how the problem may be completely solved for trapping states; i.e., we find (exact) eigenstates of the full Hamiltonian. We show how, in the low intensity regime, Jaynes–Cummings and anti-Jaynes–Cummings interactions may be obtained, without using the rotating wave approximation and analyze the medium and high intensity regimes where dispersive Hamiltonians are produced. The traditional approach (low intensity regime) is also studied and used for the generation of non-classical states of the vibrational wavefunction. In particular, we show how to add and subtract vibrational quanta to an initial state, how to produce specific superpositions of number states and how to generate NOON states for the two-dimensional vibration of the ion. It is also shown how squeezing may be measured. The time dependent problem is studied by using Lewis–Ermakov methods. We give a solution to the problem when the time dependence of the trap is considered and also analyze a specific (artificial) time dependence that produces squeezing of the initial vibrational wave function. A way to mimic the ion–laser interaction via classical optics is also introduced.     

Inclusive production of the meson in hadronic decays of the Z boson

The inclusive production rate of the ρ^±(770) vector meson in hadronic Z decays is measured with the ALEPH detector at the LEP collider. A total of 3.2 million hadronic events are selected from data recorded between 1991 and 1995. Decays of ρ^±→π⁰+π^± are reconstructed for x_E>0.05 and x_p>0.05 where x_p=p_ρ/p_beam and x_E=E_ρ/E_beam. The average ρ^± multiplicity per hadronic event is evaluated to be N(ρ^±)=2.59±0.03±0.15±0.04 where the first error is statistical and the second systematic. The third error is from the uncertainty in the extrapolation to x_p=x_E=0. The rates and differential cross-section are compared with Monte Carlo model predictions and OPAL measurements. Residual Bose–Einstein correlations are found to be an important component in the analysis.