Molecular Dynamics Simulation on Charge Transfer Relaxation between Myoglobin and Water

Dynamical processes of myoglobin after photon-excited charge transfer between Fe ion and surrounding water anion are simulated by a molecular dynamics model. The roles of Coulomb interaction effect and water effect in the relaxation process are discussed. It is found that the relaxations before and after charge transfer are similar. Strong Coulomb interactions and less water mobility decrease Coulomb energy fluctuations. An extra transferred charge of Fe ion has impact on water packing with a distance up to 0.86nm.     

Conformational changes in hemoglobin triggered by changing the iron charge

In this work the hemoglobin conformational changes induced by changing the iron charge have been studied and compared with Myoglobin. Mössbauer spectroscopy was used to follow the change of the iron conformation. In order to compare the conformational relaxation of hemoglobin and myoglobin, and to study a possible influence of the quaternary structure, an intermediate metastable state of hemoglobin has been created by low temperature X-ray irradiation of methemoglobin. The irradiation reduces the Fe(III) of the heme groups to Fe(II) Low Spin, where the water is still bound on the sixth coordination. Heating cycles performed at temperatures from 140 K to 200 K allow the molecules to overcome an activation energy barrier and to relax into a stable conformation such as deoxy-hemoglobin or carboxy-hemoglobin, if CO is present. Slightly different structures (conformational substates) reveal themselves as a distribution of energy barriers (ΔG^#). The distribution of the activation energy, for the decay of the Fe(II) Low Spin intermediate, has been fitted with a Gaussian. For comparison, published myoglobin data were re-analysed in the same way. The average energy value at characteristic temperature is very similar in case of myoglobin and hemoglobin. The larger Gaussian energy distribution for myoglobin with respect to hemoglobin shows that more conformational substates are available. This may be caused by a larger area exposed to water. In hemoglobin, part of the surface of the chains is not water accessible due to the quaternary structure.     

Ion Beam Analysis of the Annealing Behavior of Helium in Ti Films

We present a theoretical calculation finding that a spectrum from ion beam analysis will change at different stopping cross sections. This is more visible at a deeper place in the sample. Helium-contained Ti films annealed at different temperatures are prepared to gain different stopping cross sections whereby the stopping cross section will change with the helium phase states and the pressure of helium bubbles. Then ion beam analysis is used to measure the concentration of helium. It is found that the concentration curve rises greatly after the sample is annealed at 673K which reflects the increasing size of the helium bubble. The results axe consistent with that of positron annihilation radiation spectra which are performed by using a changeable energy positron beam.     

Relaxation of non-equilibrium states of myoglobin studied by Mössbauer spectroscopy

A metastable Fe(II) low-spin myoglobin complex with H₂O at the sixth coordination place has been produced by X-ray irradiation of metmyoglobin at 80 K. The relaxation into the equilibrium state of deoxymyoglobin was investigated as a function of temperature. It starts at temperatures above 140 K and cannot be understood by assuming one well-defined activation energy. The relaxation is, however, well described by assuming a Gaussian barrier height distribution.     

可见光谱法研究肌红蛋白血红素铁与金属离子相互作用(Ⅰ)

肌红蛋白(Myoglobin,Mb)是哺乳动物细胞主要是肌细胞贮存和分配氧的蛋白质, 由一条多肽链和一个血红素辅基构成,其血红素铁在氧气的传递和运输中起到关键作用。文章利用紫外-可见光谱法对肌红蛋白的血红素铁和外加金属离子M(Ⅱ)[Cu(Ⅱ), Zn(Ⅱ)和Co(Ⅱ)] 的直接相互作用进行了研究。结果发现, 金属离子M(Ⅱ)与肌红蛋白活性中心的Fe(Ⅱ)发生了直接相互作用,外加金属离子将铁离子从肌红蛋白中“拖拽”出来,形成部分空位肌红蛋白衍生物。同时研究了外界条件,如离子浓度对这种相互作用的影响,发现随着外加金属离子量的增加这种相互作用逐渐增强,其作用强度依次为Co(Ⅱ)＞Zn(Ⅱ)＞Cu(Ⅱ)。 研究证实了肌红蛋白的血红素铁与金属离子之间存在直接相互作用,并且离子浓度对这种相互作用有影响。     

Abnormal Energy Dependence of Photoluminescence Decay Time in InGaN Epilayer

We employ photoluminescence (PL) and time-resolved PL to study exciton localization effect in InGaN epilayers.By measuring the exciton decay time as a function of the monitored emission energy at different temperatures,we have found unusual behaviour of the energy dependence in the PL decay process. At low temperature, the measured PL decay time increases with the emission energy. It decreases with the emission energy at 200K, and remains nearly constant at the intermediate temperature of 12OK. We have studied the dot size effect on the radiative recombination time by calculating the temperature dependence of the exciton recombination lifetime in quantum dots, and have found that the observed behaviour can be well correlated to the exciton localization in quantum dots. This suggestion is further supported by steady state PL results.     

Synergetic effect between ion energy and sample temperature in the formation of distinct dot pattern on Si(1 1 0) by ion-sputter erosion

We observed a synergetic effect between ion energy and sample temperature in the formation of distinct dot pattern on Si(1 1 0) by Ar⁺ ion sputtering. The ion flux was 20 μA/cm², a value smaller than those used in preceding reports by one or two orders of magnitude. In experiments, the ion energy was from 1 to 5 keV, and the temperature from room temperature to 800 °C. A phase diagram indicating the ranges of ion energy and temperature within which distinct dot patterns can be achieved has been obtained. Data analyses and simulation results reveal that the synergetic effect is consistent with the effect of the Ehrlich-Schwoebel step-edge barrier, rather than the Bradley-Harper model.     

Use of the direct negative Cu ion beam deposition for the control of the properties of Cu thin film

Direct metal ion beam deposition (DMIBD) technique for Cu thin film metallization is characterized. With suitable operating conditions, secondary Cu⁻ ion yield, ion/atom arrival rate ratio, ion beam energy spreads were optimized at 15%, 0.3, and 10%, respectively.After optimization of DMIBD system, the effect of Cu ion beam energy on the resistivity, adhesion strength, and surface morphology of Cu thin film was investigated. TEM micrograph shows that the film prepared at 75 eV was polycrystalline, while the film prepared at 0 eV was vertical columnar structure.As ion beam energy is increased from 25 to 75 eV, the resistivity is decreased from 6.21 to 2.09 μΩ cm, while the critical load to cause adhesion failure was increased to about 13 N at 200 eV, which is four-times higher that that of 25 eV.     

A neutron scattering study of the vibrational modes of hydrogen in the β-phases of Pd-H,Pd-10Ag-H and Pd-20Ag-H

The localised modes associated with interstitial hydrogen in the β-phases of Pd and Pd-Ag alloys have been studied by neutron energy loss at 295K, 80K and for Pd at 30K. Their energies vary little but their widths increase significantly with temperature and silver content, an effect which is ascribed to local disorder and anharmonic contributions.     

离子注入法形成的LiTaO3平板光波导的特性分析

用能量为２．８ＭｅＶ、剂量为１．４×１０１６ｉｏｎ／ｃｍ２的Ｈｅ＋在室温（３００Ｋ）下注入到晶体材料ＬｉＴａＯ３中，形成了离子注入平板光波导。用棱镜耦合法观察和测量了ＬｉＴａＯ３波导导模的分布，并对退火前后的ＬｉＴａＯ３波导的折射率分布进行了计算和比较。利用背散射／沟道技术分析了由于Ｈｅ＋的注入而引起的波导表面的损伤。     

Ion temperature and hydrodynamic-energy measurements in a Z-pinch plasma at stagnation

The time history of the local ion kinetic energy in a stagnating plasma was determined from Doppler-dominated line shapes. Using independent determination of the plasma properties for the same plasma region, the data allowed for inferring the time-dependent ion temperature, and for discriminating the temperature from the total ion kinetic energy. It is found that throughout most of the stagnation period the ion thermal energy constitutes a small fraction of the total ion kinetic energy; the latter is dominated by hydrodynamic motion. Both the ion hydrodynamic and thermal energies are observed to decrease to the electron thermal energy by the end of the stagnation period. It is confirmed that the total ion kinetic energy available at the stagnating plasma and the total radiation emitted are in balance, as obtained in our previous experiment. The dissipation time of the hydrodynamic energy thus appears to determine the duration (and power) of the K emission.     

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (−1.15 eV) and charge recombination reaction (−1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.     

Anomalous ion accelerated bulk diffusion of interstitial nitrogen

Interstitial N diffusion under low energy (approximately 700 eV) Ar+ bombardment at 673 K in ion beam nitrided austenitic stainless steel is investigated. Ar+ ion bombardment increases the N mobility in depths far beyond the ion penetration depth, resulting in an increased broadening of the N depth profile as a function of Ar+ flux. This effect cannot be explained by any established mechanism of radiation-enhanced diffusion. An explanation based on quasiparticle-enhanced mobility is proposed.     

On the Urbach rule in sulphur-implanted Cu6PS5I superionic conductors

Cu₆PS₅I superionic crystals, grown using chemical vapour transport, were implanted by sulphur ions. The ion implantation effect on the phase transitions is studied by temperature isoabsorption investigation of the optical absorption edge. For the implanted crystals the optical absorption edge shape is studied in the temperature range 77-320 K, the parameters of exciton-phonon interaction, resulting in the Urbach behaviour of the optical absorption edge, are determined, the temperature dependences of the optical pseudogap and Urbach energy are obtained. The implantation effect on the ordering-disordering processes in Cu₆PS₅I superionic conductors is studied.     

Concentrations and velocity distributions of positive ions in laser ablation of copper

It is shown that the generation of secondary electrons by excited neutrals hitting a surface makes the so-called probe method unsuited for measuring the positive ion fraction in laser ablation plumes. Experiments have been performed in a modified set-up, in which the disturbance by secondary electrons is avoided. For a typical case of Cu irradiated in ultra-high vacuum by nanosecond excimer laser pulses of 3 J cm^–2 the ionized fraction is about 10^–8 at a distance of 60 cm. This number is in fair agreement with Saha-Langmuir predictions based on the assumption of local thermal equilibrium at an estimated temperature of about 3000K. Angular-resolved time-of-flight measurements show that there are three different ion velocity distributions. A slow contribution (kinetic energy 2eV) with an angular distribution peaked along the normal, and two fast, isotropic contributions (kinetic energy 20–50 eV). The fast contributions are attributed to ions involved in a Coulomb explosion.     

Anomalous conductivity effects in (Na,K) mixed crystals of the β-Al2O3 type

Anomalous behavior has been observed in the ionic conductivity of (Na,K) mixed crystals of the alkali gallates and aluminate of the β-Al₂O₃ type fast ion conductors. The conductivity goes through a minimum at some intermediate composition as a consequence of a maximum in the activation energy, and is most pronounced in the (Na,K)-β-gallate, followed by (Na,K)-β-Al₂O₃ and (Na,K)-β“-gallate. The effect is similar to the well-known “mixed alkali effect” in glasses. A second anomaly consisting of a pronounced increase in conductivity over about a 70° temperature range, without any permanent change in activation energy, was observed for some compositions of (Na,K)-β“-gallate.     

High-energy heavy-ion induced physical and surface-chemical modifications in polycrystalline cadmium sulfide thin films

The effect of high electronic energy deposition on the structure, surface topography, optical properties, and electronic structure of cadmium sulfide (CdS) thin films have been investigated by irradiating the films with 100 MeV Ag⁺⁷ ions at different ion fluences in the range of 10¹²–10¹³ ions/cm². The CdS films were deposited on glass substrate by thermal evaporation, and the films studied in the present work are polycrystalline with crystallites preferentially oriented along (002)-H direction. It is shown that swift heavy ion (SHI) irradiation leads to grain agglomeration and hence an increase in the grain size at low ion fluences. The observed lattice compaction was related to irradiation induced polygonization. The optical band gap energy decreased after irradiation, possibly due to the combined effect of change in the grain size and in the creation of intermediate energy levels. Enhanced nonradiative recombination via additional deep levels, introduced by SHI irradiation was noticed from photoluminescence (PL) analysis. A shift in the core levels associated with the change in Fermi level position was realized from XPS analysis. The chemistry of CdS film surface was studied which showed profound chemisorption of oxygen on the surface of CdS.     

Entrance-Channel Dependence of Isospin Effects on Double n/p Ratio in HIC

Within the hadronic transport model IBUU04, we investigate the effect of density-dependent symmetry energy on double neutron/proton (n/p) ratio of free nucleons in heavy ion collisions by taking four isotopic Sn+Sn reaction systems. Especially the entrance-channel asymmetry and impact-parameter dependence of the effect of symmetry energy are discussed. It is found that in both central and semi-central collisions the sensitivity of the double n/p ratio to the density-dependent symmetry energy is more pronounced in neutron-richer systems. Our results also indicate clearly that the effect of symmetry energy is stronger in central collisions than that in semi-central collisions.     

Ripening of subsurface amorphous C clusters formed by low energy He ion bombardment of graphite

Surfaces of highly oriented pyrolytic graphite (HOPG) were bombarded with 100 eV and 500 eV He ions at ion doses of a few 10¹⁵ cm² and temperatures ranging from 300 K to 800 K. AFM images were recorded to investigate the topography of the surfaces after ion bombardment. Supplementary electron energy loss (EEL) and thermal desorption (TD) spectra were measured to determine the C sp² fraction of the bombarded surfaces and the amount of trapped He. The temperature at which He ion bombardment was performed had a drastic effect on the surface structure and topography of the targets on the angstrom-scale and micrometer-scale as well. At 300 K, limited defect atom transport revealed an amorphous but relatively flat HOPG surface. Bombardment at 400 K leads to a granular structure of small protrusions in micrometer-scale AFM images, however, without crystalline order on the surface. The protrusions are due to the formation of subsurface clusters of carbon formed by atoms displaced by ion irradiation. Towards higher temperatures during bombardment the clusters agglomerate and cause the surface layers to bend upwards in dome-like shapes. Simultaneously, the microscopic order of the graphite lattice recovers. At 800 K large areas of the top layer retain their order during bombardment, however, a small number of domes indicate that there still exist some subsurface C clusters. The cluster–cluster distance deduced from the dome distribution indicates that the clusters grow through a ripening process. Annealing of graphite at high temperatures subsequent to ion bombardment at low temperatures is much less effective for recovering the surface crystallinity than ion bombardment at high temperature.     

Li and K NMR relaxation study of a LiKSO4 single crystal

The ⁷Li and ³⁹K NMR relaxations in a LiKSO₄ single crystal grown by the slow evaporation method were investigated by employing a pulse NMR spectrometer. From the experimental data, the quadrupole coupling constant and asymmetry parameter were determined at the temperatures of 180 and 300 K. The relaxation processes of ⁷Li and ³⁹K were studied for the LiKSO₄ crystal, and the relaxation times for the ⁷Li and ³⁹K nuclei exhibit remarkable changes near T_c2 (=190 K). The activation energies for ⁷Li and ³⁹K were determined in phases I and III. The large change in the activation energy at 190 K indicates that the Li and K ions are significantly affected during this transition. The correlation time of the ⁷Li calculated from the spin-lattice relaxation time and quadrupole parameters was larger than that of the ³⁹K calculated using the same method. The reason for this is that the Li ion undergoes molecular motion as in the LiO₄ groups.