Change in free volume of polyvinylidene fluoride

Measurement of positron lifetime was carried out on polyvinylidene fluoride as a function of temperature ranging from 193 to 293 K. The local molecular motion, the cooperative motion of long chain, and the thermal expansion are discussed based on the change in free volume concluded with the use of positron lifetime. The different temperature dependence of motions is suggested for an amorphous area constrained by crystalline regions and a free amorphous area.     

SACM/CT Study of the dissociation/recombination dynamics of hydrogen peroxide on an ab initio potential energy surface. Part II. Specific rate constants k(E,J), thermal rate constants k infinity(T), and lifetime distributions

Statistical adiabatic channel model/classical trajectory (SACM/CT) calculations of the dissociation/recombination dynamics of hydrogen peroxide, H(2)O(2) <--> 2HO, have been performed on an ab initio potential energy surface by Kuhn, Rizzo, Luckhaus, Quack, and Suhm (J. Chem. Phys. 1999, 111, 2565). Specific rate constants k(E,J), thermal rate constants k(infinity)(T), and lifetime distributions are determined. After averaging over J, the derived k(E,J) are in quantitative agreement with non-exponential time-profiles of HO formation recorded after overtone excitation of H(2)O(2) near the dissociation threshold by Scherer and Zewail (J. Chem. Phys. 1987, 87, 97). The thermal high pressure rate constants for HO recombination agree with experimental data as well and can be represented by k(rec,infinity)/10(-10) cm(3) molecule(-1) s(-1) approximately [0.376 (298 K/T)(0.47) + 0.013 (T/298 K)(0.74)] over the range 60-1500 K. Non-statistical lifetime distributions are suggested not to have been of major relevance for the available experiment.     

35S atoms in liquid chlorinated organic compounds

The lifetime spectra of positrons in solid chrysene were measured at temperatures of 160–300 K. The temperature dependence of positronium yield suggests Ps trapping on thermally produced free volumes. Those volumes cannot be vacancies, but rather the intermolecular free spaces; thermal motions of molecules can increase these spaces to the extent making Ps creation energetically possible.     

Ab initio and direct dynamics study of the reaction of Cl atoms with HOCO

The reaction of Cl with HOCO has been examined using the coupled-cluster method to locate and optimize the critical points on the ground-state potential energy surface. The results show that the reaction produces the HCl and CO(2) products as experimentally observed. The reaction occurs via a HOC(O)Cl intermediate with an estimated heat of formation of -97.8+/-2.0 kcal/mol. A direct ab initio dynamics method has been used to provide insight into the reaction mechanisms and to determine the thermal rate coefficients in the temperature range of 200-600 K. At room temperature, the thermal rate coefficient is predicted to be 3.0x10(-11) cm(3) molecule(-1) s(-1) with an activation energy of -0.2 kcal/mol. Two kinds of reactive trajectories are found. One kind proceeds through short-lived HOC(O)Cl complexes with a lifetime of 310 fs while the other kind occurs via longer-lived intermediates with a lifetime of 1.9 ps.     

Influence of base dynamics on the conformational properties of DNA: Observation of static conformational states in rigid duplexes at 77 K

Time-resolved fluorescence of 2-aminopurine-labeled DNA duplexes at 77 K reveals the relationship between base dynamics and the conformational heterogeneity that results in the well-known multiexponential fluorescence decay at room temperature. The conformation that exhibits rapid interbase charge transfer at room temperature is not populated in the frozen duplex at 77 K; this geometry is accessed by thermal motion of the bases, it is not a minimum energy structure of the duplex. Three photophysically distinct conformational states persist in the frozen duplex; these are minimum energy structures and do not interconvert at room temperature on the time scale of the 2-aminopurine excited-state lifetime.     

Luminescence interference-free lifetime nanothermometry pinpoints in vivo temperature

Luminescence nanothermometry makes non-invasive and real-time temperature readings possible in living animals. However,the spectral fluctuation in tissues and fluids, as well as the interaction between fluorophores and environment hinders accuracy of the thermometry. Here, we report a luminescence lifetime-based nanothermometry which specifically addresses this problem. A temporal based calibration(lifetime sensing) in the NIR range, an endogenous thermal response as well as a polymer encapsulation evading environmental factors, altogether help to pinpoint temperature in vivo. Thanks to the highly condensed NdYb ions in a well-protected tiny core-shell nanocrystal(overall 11 nm), a temperature sensitivity about 2.07% K~(-1)(with 5% Yb~(3+) doped nanoparticles) and an accuracy of 0.27 K(with 25% Yb~(3+) doped nanoparticles) in biological fluids are achieved.Hopefully, combining thermally activated energy transfer nanothermometer with anti-interference lifetime thermometry would provide a more accurate temperature measurement for biological and preclinical studies.     

Template transformations in preparation of MCM-41 silica

Template transformation in MCM-41 material during thermal treatment under different conditions was investigated on the basis of thermogravimetry (TG-DTA), X-ray diffraction (XRD) and positron annihilation lifetime spectroscopy (PALS). Micelle templated silica was prepared using C18 trimethylammonium bromide. The pore structure of MCM-41 samples obtained after removal of the surfactant in air, argon flow and vacuum was analyzed on the basis of the adsorption isotherms of nitrogen at 77 K and XRD experiments. The TG-DTA experiments confirm the mechanism of the template removal known from literature. However, the sequence of the processes during thermal treatment of as-synthesized sample and temperature of transformations depended strongly on the presence of oxygen and the heating rate. The main template degradation took place below 573 K and was independent of the kind of atmosphere above the sample. Residual carbonaceous species are removed from pores and the external surface of MCM-41 silica upon heating to 823 K by combustion or evaporation. The latter process as well as translocation of liquid-like products of template degradation from the pore interior to external surface was confirmed by PALS experiment in vacuum.     

Free volume in imidazolium triflimide ([C3MIM][NTf2]) ionic liquid from positron lifetime: amorphous, crystalline, and liquid states

Positron annihilation lifetime spectroscopy (PALS) is used to study the ionic liquid 1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide [C(3)MIM][NTf(2)] in the temperature range between 150 and 320 K. The positron decay spectra are analyzed using the routine LifeTime-9.0 and the size distribution of local free volumes (subnanometer-size holes) is calculated. This distribution is in good agreement with Fürth's classical hole theory of liquids when taking into account Fürth's hole coalescence hypothesis. During cooling, the liquid sample remains in a supercooled, amorphous state and shows the glass transition in the ortho-positronium (o-Ps) lifetime at 187 K. The mean hole volume varies between 70 ?(3) at 150 K and 250 ?(3) at 265-300 K. From a comparison with the macroscopic volume, the hole density is estimated to be constant at 0.20×10(21) g(-1) corresponding to 0.30 nm(-3) at 265 K. The hole free volume fraction varies from 0.023 at 185 K to 0.073 at T(m)+12 K=265 K and can be estimated to be 0.17 at 430 K. It is shown that the viscosity follows perfectly the Cohen-Turnbull free volume theory when using the free volume determined here. The heating run clearly shows crystallization at 200 K by an abrupt decrease in the mean <τ(3)> and standard deviation σ(3) of the o-Ps lifetime distribution and an increase in the o-Ps intensity I(3). The parameters of the second lifetime component <τ(2)> and σ(2) behave parallel to the o-Ps parameters, which also shows the positron's (e(+)) response to structural changes. During melting at 253 K, all lifetime parameters recover to the initial values of the liquid. An abrupt decrease in I(3) is attributed to the solvation of e(-) and e(+) particles. Different possible interpretations of the o-Ps lifetime in the crystalline state are briefly discussed.     

聚芳醚醚酮的热老化寿命研究

本工作用热重法(TG)研究了聚芳醚醚酮(PEEK)在空气和氮气中的热分解反应过程;确定了PEEK在这两种气氛中的热分解反应模型均符合无规引发断裂模型;在空气中PEEK的热分解显示两个过程,由此计算其在空气中第一阶段的热分解和氮气中的热分解反应活化能分别为214.7kJ/mol和232.2kJ/mol;由热分解反应动力学参数推算出热老化寿命曲线,并讨论了实验条件对结果的影响,进而以失重5%作为材料寿终指标估算出PEEK在氮气和空气中使用10年的最高温度分别为307℃和274℃。     

Temperature-dependent helix-coil transition of an alanine based peptide

The helix-coil transition of a synthetic alpha-helical peptide (the D-Arg peptide), Ac-YGG(KAAAA)(3)-CO-D-Arg-CONH(2), was studied by static far-UV circular dichroism (CD) and time-resolved infrared spectroscopy coupled with the laser-induced temperature-jump technique for rapid relaxation initiation. Equilibrium thermal unfolding measurements of the D-Arg peptide monitored by CD spectroscopy reveal an apparent two-state helix-coil transition, with a thermal melting temperature around 10 degrees C. Time-resolved infrared (IR) measurements following a laser-induced temperature jump, however, reveal biphasic (or multiphasic) relaxation kinetics. The fast phase rises within the 20 ns response time of the detection system. The slow phase has a decay lifetime of approximately 140 ns at 300 K and exhibits monotonic temperature dependence with an apparent activation energy around 15.5 kcal/mol.     

Differentiation of the local structure around tryptophan 51 and 64 in recombinant human erythropoietin by tryptophan phosphorescence

Abstract Recombinant human erythropoietin is a 4-helix bundle, glycosylated cytokine containing three tryptophan residues at positions 51, 64 and 88 whose phosphorescence emission may represent a sensitive probe of the structure at multiple sites near or at the protein surface. This report characterizes the phosphorescence properties (spectral energy, thermal spectral relaxation and phosphorescence lifetime), from low temperature glasses to ambient temperature, of the native protein plus that of three single point mutation analogs where each Trp was replaced by Phe. The structural information inferred from the phosphorescence parameters was essentially in good agreement with the structure of the Escherichia coli-produced nonglycosylated protein determined by nuclear magnetic resonance (Cheetham et al., Nat Struct Biol [1998] 5:861). The results showed that the fluorescence and phosphorescence spectra of the native protein were entirely due to independent contributions of Trp51 and Trp64 and that Trp88 was quenched under all conditions. The phosphorescence emissions of Trp51 and Trp64 were differentiated by their unique spectra at 77 K with Trp64 exhibiting an unusually blueshifted spectrum likely due to the attractive interaction of Arg110 and Lys116 with the ground state dipole of Trp64. In the native protein the room temperature phosphorescence lifetime of Trp64 was relatively short with a time of 1.62 ms whereas the lifetime of Trp51 was five-fold longer. Characterization of the single point mutation analogs showed that each lifetime was composed of multiple components revealing the presence of multiple stable conformations of the protein at these surface sites.     

Temperature dependence of positron lifetime in ordered porous silica (SBA-3)

The temperature dependence of positron lifetime in uniform mesopores was analyzed. We used SBA-3 as the sample material, which possesses an ordered porous structure with uniform cylindrical mesopores. The positron lifetime corresponding to the annihilation in the mesopores increased gradually with a decrease in temperature down to 100 K, and its relative intensity also increased concomitantly. This result was attributed to the lower probability of the escape of the ortho-positronium (o-Ps) from the mesopores into the intergrain space at lower temperatures. An anomalous and sudden increase in the lifetime was observed at around 100 K; this result was in agreement with an increase in the positron lifetime reported in a previous study. It was revealed that the increase in the lifetime is very steep in cases of uniform mesopores, suggesting that the temperature dependence is influenced by the pore size.     

Infrared spectroscopy of physisorbed and chemisorbed O2 on Pt(111)

The adsorption of O2 on the Pt(111) surface, with particular emphasis on the influence of substrate temperature, has been studied by infrared reflection absorption spectroscopy (IRAS). In the temperature range 30-90 K the IRAS spectra reveal three different molecular adsorption states. A physisorbed state appears below 40 K while chemisorbed peroxo- and superoxo-like states are observed in the whole temperature range, the characteristic vibrational frequencies are at full coverages of 16O2, 1543 cm(-1) and around 700 cm(-1) and 870 cm(-1), respectively. Flash heating from 30 K to 45 K reveal that the physisorbed state acts as a precursor to the superoxo chemisorption. Theoretical calculations suggest that peroxo molecules may occupy both fcc and hcp threefold sites on the Pt(111) surface. However, within the high resolution of the IRAS measurements we only observe one peroxo state in the temperature range 45-90 K, assigned to occupy the fcc site. The peroxo adsorption probability is significantly lower at 45 K than at 90 K, presumably due to reduced thermal activation from the physisorbed precursor state. A longer lifetime in this precursor state at the low temperature results in formation of larger superoxo islands already at low oxygen coverage.     

Anisotropic fluorescence of Michler's ketone in liquid solutions

In solutions of Michler's ketone in ethanol at 295 K, the fluorescence is almost completely anisotropic. This phenomenon is caused by the unusually short lifetime of the excited singlet state due to a short intrinsic lifetime and processes leading to a very low quantum yield. The absorption, fluorescence and phosphorescence spectra, their degree of anisotropy and the values of the quantum yield at 295 K, 203 K and 100 K are reported.     

Fluorescence properties of fluoranthene as a function of temperature and environment

The fluoranthene fluorescence properties were investigated in a variety of environments, i.e. in different solvents and temperatures, in the solid state, and in the vapor phase. The emission maximum was found to be independent of environment. The absorption spectrum in different solvents exhibits only minor changes. In solution, the fluorescence lifetime shows a slight inverse relationship to the solvent dielectric constant. With water/methanol mixtures of varying composition as the solvent, the lifetime decreases linearly with increasing mole fraction of water. At 77K, the fluoranthene fluorescence lifetime in frozen polar and nonpolar solvents are the same within experimental error. In hexane the fluorescence lifetime is independent of temperature (77±3 and 82±7 ns, at room temperature and 77 K, respectively). In methanol the lifetime is 64±3 ns at room temperature and increases linearly to 80±4 ns at 77 K. In the vapor phase the lifetime is 32±1 ns. No fluorescence quantum yield change was observed for either S₁ or S₂ manifold excitation.     

Thermal stability of high temperature epoxy adhesives by thermogravimetric and adhesive strength measurements

The thermal degradation of two high temperature epoxy adhesives has been measured in terms of weight loss and adhesion loss and the lifetime predictions are compared for the two independent measurements of thermal degradation. Weight loss measurements were performed at high temperature under accelerated thermal aging conditions. Adhesion loss measurements were performed at lower temperatures closer to typical continuous operating temperatures. An Arrhenius relationship is validated for the thermal degradation of the epoxy adhesives, and the extent of degradation in terms of weight loss and adhesion loss is modelled with an autocatalytic rate expression. The degradation kinetic parameters and models are compared between the two thermal degradation measurements and are found to give similar predictions for the lifetime of the adhesives. In addition, the relationship between network degradation and loss of adhesive strength is discussed.     

等温热重法研究新型尾式卟啉季铵盐的热稳定性及寿命

用等温热重技术研究了三种新型尾式卟啉-三乙胺和吡啶季铵盐的热稳定性及寿命。得到了失重10%为寿终指标的寿命方程及稳定性大小的顺序。     

Thermal variation of free-volumes size distribution in polypropylenes. Probed by positron annihilation lifetime technique

Positron annihilation lifetime measurement was applied to the study of free-volume properties in three kinds of polypropylene as a function of temperature in the range of 25–180°C at thermal equilibrium. Positron lifetime data for polypropylenes were analyzed with a Laplace inversion technique in order to obtain continuous positron annihilation lifetime (PAL) distributions. At each temperature, four distinct PAL distributions were recognized. The distribution of the longest lived component was associated with a pick-off annihilation of ortho-positronium (o-Ps) trapped in free-volume of amorphous region, which grew bigger as the temperature increased. The hole radius distributions of free-volumes were estimated from the results of o-Ps lifetime distributions. A detailed analysis showed a mean radius of free volumes was 0.34 nm at room temperature and that was 0.42 nm near the melting point for each specimen. The distributions of hole radii of free volumes were found to be broader after thermal treatments. The relaxation of free volumes was attributed to the thermal equilibrium and the evacuation of included molecules in free volumes. © 1995 John Wiley & Sons, Inc.     

A positron annihilation lifetime study of isotactic polypropylene

Positron lifetime studies were performed on well-characterized annealed and quenched samples of isotactic polypropylene. The positron experiments were conducted from ?20 to 110°C as a function of both heating and cooling. Of the three decaying exponential components resolved from the lifetime spectra, only the long-lifetime ortho-positronium (o-Ps) pickoff component was affected by the changes in temperature. The behavior of both the lifetime and intensity of the o-Ps component was interpreted with the aid of x-ray diffraction, densitometry, and optical microscopy examinations and results from previously reported investigations of the thermal transition behavior of polypropylene. The present experiments demonstrate that o-Ps lifetimes were similar for both the annealed and quenched samples, independent of thermal cycling, while the o-Ps component intensity was significantly larger for the quenched material during heating, with both sample types exhibiting a significant hysteresis upon cooling. These results suggest that the mean free-volume cavity size is independent of prior thermal treatment, while the density of free-volume sites is a sensitive function of structure and prior thermal history. The variations of lifetime and of intensity with temperature have provided insight into polypropylene's glass transition phenomena.     

Quantum scattering calculation of the O(1D)+HBr reaction

Three-dimensional time-dependent quantum wave packet calculation for the O((1)D)+HBr reaction has been carried out using an accurate ab initio global potential energy surface [K. A. Peterson, J. Chem. Phys. 113, 4598 (2000)]. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.