Kinetic and thermodynamic considerations of the bracketing method: Entropy-driven proton-transfer reactions in a Fourier transform mass spectrometer

Several reports of experimentally derived proton affinity values and gas-phase basicity values for amino acids and peptides have recently appeared in the literature. Here, we show that the thermodynamic quantity that is measured by the Fourier transform mass spectrometry proton transfer bracketing of amino acids and peptides is gas-phase basicity and not proton affinity. Both experimental and theoretical evidence supports this conclusion. The difference between the values determined by proton transfer bracketing measurements for lysine versus leucine is consistent with a difference in gas-phase basicity rather than proton affinity. The rate of proton transfer from protonated lysine to a series of reference compounds have been measured. Entropy-driven, endothermic proton transfer is found to occur at the collision rate. Recent ab initio and semi-empirical calculations of the proton affinity of lysine are found to agree with the value that is derived from bracketing studies when one assumes that gas-phase basicity is measured. While entropy-driven reactions have been observed previously in high-pressure mass spectrometers, this is the first evidence for such reactions at low pressure in a Fourier transform mass spectrometer.     

Invariants of chaotic Hamiltonian systems

The invariants of chaotic bounded Hamiltonian systems and their relation to the solutions of the first variational equations of the equations of motion are studied. We show that these invariants are characterized by the fact that they either lose the property of differentiability as functions on phase space or that a certain formal power series defined in terms of the derivatives of the invariants has zero radius of convergence. For a specific example, we show that the former possibility appears to apply.     

纳米硅薄膜光吸收谱的研究

用恒定光电导法测量了纳米硅(其晶粒尺寸为3-5nm,晶态成分比X_c为45％—50％)薄膜在0.9—2.5eV范围的光吸收谱。分析了在不同光子能量范围可能存在的对光电导作主要贡献的几种光跃迁过程,以及随着X_c的增加,材料由非晶、微晶转变为纳米硅薄膜时光吸收谱的变化。发现纳米硅晶粒之间的界面区(平均厚度约为1nm)中载流子的跃迁及传输过程对整个范围的光吸收谱起主导作用。联系纳米硅的这种特殊结构解释了有关实验结果。 关键词：     

A high performance liquid chromatographic assay for AMP-deaminase activity in the erythrocytes of healthy subjects and patients with inherited purine disorders

A novel method for measuring AMP-deaminase activity in human erythrocytes is presented, based on the determination of the reaction product, IMP, using high performance liquid chromatography. IMP formation was found to be proportional both to the incubation time and the amount of haemolysate over a wide range. The minimal detectable AMP-deaminase activity was more than 1000 times lower than the mean activity found in healthy controls (1083 nmol/h/mg Hb). No marked difference of activity was found in the patients with the following inherited purine disorders: familial juvenile gouty nephropathy and deficiencies of adenosine deaminase, hypoxanthine-guanine phosphoribosyltransferase or adenine phosphoribosyltransferase. The activity in the erythrocytes of patients with chronic renal failure was also similar to controls. The existence of subjects with low erythrocyte AMP-deaminase activity in the population has been confirmed.     

Inclusive (γ, N), (γ, NN) and (γ, Nπ) reactions in nuclei at intermediate energies

Differential cross sections of nucleons excited in photonuclear reactions in medium and heavy nuclei are studied by considering all relevant reaction mechanisms leading to the excitation of protons or neutrons. We take advantage of previous microscopic studies for the absorption and scattering of photons and photoproduced pions, and implement a simulation code in order to take into account the propagation of the nucleons as well as their collisions with other nucleons in the nuclear medium, which generate secondary excited nucleons. Comparison with experimental data is done. Cross sections for nucleon emission in coincidence with one pion are also calculated, and some coincidence observables are discussed.     

The Coherent-Path Model for Nuclear Resonant Gamma-Ray Scattering: An Overview

Hyperfine Interactions - A “coherent-path” model for nuclear-resonant scattering of gamma radiation from resonant matter has been developed and is summarized here. The solution provides...     

Zeeman transitions in deuterium atoms induced by ultra-relativistic electrons

We present data showing hyperfine transitions in an atomic deuterium beam induced by the (476 MHz) radio-frequency field of a 704 MeV electron beam in a storage ring. A polarized deuterium beam, produced in an atomic beam source, was crossed with a stored electron beam and analyzed with a Breit--Rabi polarimeter. Electron-beam induced transitions were singled out by injecting different combinations of hyperfine states. Transition probabilities as high as 70% were measured at large currents (~ 100 mA). All possible deuterium transitions for a radio-frequency of 476 MHz were observed. In addition, a 1--6 transition resulting from the first harmonic (952 MHz) was observed. The effects of these transitions are of general importance for the polarized internal target technique applied in nuclear and particle physics experiments. The data are reasonably described by numerical estimates. The observed mechanism can be exploited to create nuclear polarized atoms when injecting electron polarized atoms with no net nuclear polarization into a storage cell. However, when nuclear polarized atoms are injected, care should be taken to avoid this mechanism, since it would result in depolarization of the atoms. The studies enabled us to choose the magnetic guide field during our spin-dependent electron--deuteron scattering experiments, such that electron-beam induced depolarizing effects were avoided. This revised version was published online in July 2006 with corrections to the Cover Date.     

Lifetime study of high-spin states in 104,105In

In the neutron deficient isotopes _104,105In lifetimes of high spin states in the range from 0.5 ps to 600 ps have been measured in a coincidence recoil distance Doppler shift (RDDS) experiment. By combining the Doppler shift attenuation (DSA) and RDDS methods at few μm flight distances, the problem of delayed feeding has been avoided and very short lifetimes in the range 0.5–0.8 ps have been determined. Shell model calculations with strong restrictions for the neutron orbitals reveal good agreement with experimental level energies and still fair agreement for most measured B(M1) and B(E2) values. Received: 30 June 1998