三元乙丙橡胶玻璃化转变温度以上的Sub-Rouse弛豫峰研究

采用动态力学分析法(DMA)研究了三元乙丙橡胶(EPDM)的链段弛豫行为.结果表明随着温度的升高,EPDM样品依次出现了3个内耗弛豫峰,分别是玻璃化转变(α转变)、sub-Rouse模式转变(α'转变)和Rouse模式转变(α″转变).通过分析频率谱中弛豫时间、弛豫强度、耦合参数和形状因子分别随温度的变化,发现在温度为384 K处,sub-Rouse模式转变存在动态转折点TB.而且,转折点的弛豫时间τα'(TB)大约是0.11 s,这与文献报道的PS及PVAc/PEO共混物(10(-0.5±0.5)s)等材料的弛豫时间非常接近,表明该转折点是在特定的弛豫时间产生的.基于链段耦合模型,我们提出此转折点是由低于TB温度时分子间耦合增强引起的.     

无机盐对乙醇-水体系LF-NMR弛豫特性的影响及主成分分析

该文研究了不同浓度(0~9%)的Na Cl,Mg SO4或Na OH对乙醇-水体系LF-NMR弛豫特性的影响,并应用主成分分析(PCA)对样品的弛豫特性进行了分析。研究表明:无机盐种类和浓度会对水及乙醇-水体系的LF-NMR弛豫特性产生影响。无机盐-水二元体系仅存在1个弛豫峰,且弛豫时间:Mg SO4Na OHNa Cl。而无机盐-乙醇-水三元体系则存在2个弛豫峰,Na Cl/Na OH-乙醇-水体系的弛豫峰分别位于200~330 ms和1 300~1 600 ms处;而Mg SO4-乙醇-水体系则位于约250~335 ms和1 620~1 707 ms处。不同种类无机盐、水和乙醇-水体系间的LF-NMR弛豫特性差异均可在PCA得分图上有效反映,且随着无机盐浓度的增加,各浓度梯度在主成分得分图中亦呈规律性分布。说明基于样品的LF-NMR弛豫特性,结合主成分分析法可快速分析无机盐对水/乙醇-水的缔合特性。     

阴离子表面活性剂SDBS胶束溶液的介电弛豫行为

用射频介电谱方法研究了0.1-80 mmol·L-1浓度的十二烷基苯磺酸钠(SDBS)水溶液体系的介质弛豫行为. 测量发现频率接近107 Hz时, 在临界胶束浓度(CMC)附近出现显著的介电弛豫现象. 采用Cole-Cole函数拟合SDBS体系介电数据, 其拟合参数具有明显变化规律: 介电增量(△ε)随SDBS摩尔浓度(cs)的增加而增大, 表现为两种线性关系, 并在cs=36 mmol·L-1附近出现拐点; 特征弛豫时间(τ0)却在cs=45 mmol·L-1出现极小值. 利用胶束电模型分析了介电弛豫机制, 认为束缚Na+对离子数量和胶束体积变化是引起介电增量和特征弛豫时间变化的两个重要原因.     

聚甲基乙烯基硅氧烷/炭黑复合体系的电阻弛豫行为

考察了聚甲基乙烯基硅氧烷/炭黑(CB)复合交联体系在恒定压应力作用下以及完全卸载后的导电行为,发现电阻在恒定压应力作用下及完全卸载后均随时间非线性下降,呈现典型的电阻弛豫行为.根据电阻弛豫时间以及最大电阻弛豫幅度,分析了导电网络结构变化与电阻弛豫之间的关联,讨论了炭黑含量对电阻弛豫的影响.结果表明,在恒定压应力2~4MPa下,电阻弛豫具有两个与CB含量无关的弛豫时间,对应不同尺寸导电网络的结构变化.完全卸载后,基体形变回复造成导电网络发生结构弛豫,弛豫时间随CB含量增大而延长.     

CeO2陶瓷的介电频响研究

研究了CeO_2陶瓷室温下低频和射频的介电谱,并给出了介电常数和介质损耗及其与温度的关系。测量结果表明,此种陶瓷存在弛豫极化,其偶极子的弛豫时间约为5×10~(-9)S。在330℃以下,CeO_2陶瓷的介电常数和介质损耗具有良好的温度特性。在室温下,CeO_2陶瓷在500kHz～50MHz频率范围内具有良好的介电特性。     

低场核磁共振技术测定顺磁性钆(Ⅲ)和钕(Ⅲ)

利用长弛豫低场核磁共振技术分别测定了六水合氯化钆水溶液、N,N-二甲基甲酰胺(DMF)溶液和六水合硝酸钕水溶液在不同浓度下的横向弛豫时间(T_2)。3种溶液体系中氢质子的横向弛豫速率(1/T2)与稀土离子的浓度均呈现出良好的线性关系,提出了利用低场核磁技术测定溶液中Gd~(3+)和Nd~(3+)浓度的方法。     

离子交换树脂悬浊液的介电弛豫谱研究

研究了D354阴离子交换树脂分散在不同浓度KCl溶液中的悬浊液的频率域介电谱,发现在测量频率为106～107 Hz处出现了显著的介电弛豫现象,得出了介电常数、电导率以及弛豫时间随KCl溶液浓度的特异的变化关系,理论分析表明,该弛豫是一个以界面极化为主的非单一极化机制的弛豫过程,进而利用Maxwell-Wagner界面极化理论和双电层性质解释了该体系的特异介电行为,得到了树脂悬浊液在外加交变电场下的离子迁移和聚集信息,并确定了该树脂在静态平衡下双电层中对离子的相对离子强度.     

浓差极化的介电模型——复合膜/溶液体系的数值模拟

提出了具有电导率和介电常数线性分布的介质的介电模型, 并导出了其内部电的和结构性质的参数与宏观测量的电容和电导之间定量关系的理论表达式, 以模拟复合膜中的多孔层部分的介电弛豫行为. 大量的模拟计算描述并解释了多孔层介电谱随介电常数分布、厚度等性质而变化的规律. 进一步对具有层状构造的复合膜以及复合膜和溶液相组成的多层体系的弛豫行为进行了数值模拟, 比较了三个体系(多孔层、复合膜、复合膜/液相层状体系)的介电谱, 结果揭示了介电谱对各层性质的依赖关系. 所提出的电导率和介电常数线性分布的多孔层的介电模型, 也可用于具有其他电导率、介电常数分布规律的体系.     

丙烯酸分子的激发态超快预解离动力学

利用飞秒泵浦-探测技术结合飞行时间质谱(TOF-MS),研究了丙烯酸分子被200nm泵浦光激发到第二电子激发态(S2)后的超快预解离动力学.采集了母体离子和碎片离子的时间分辨质谱信号,并利用动力学方程对时间分辨离子质谱信号进行拟合和分析,揭示了预解离通道的存在.布居在S2激发态的分子通过快速的内转换弛豫到第一电子激发态(S1),时间常数为210fs,随后再经内转换从S1态弛豫到基态(S0)的高振动态,时间常数为1.49ps.分子最终在基态高振动态势能面上发生C-C键和C-O键的断裂,分别解离生成H2C=CH和HOCO、H2C=CHCO和OH中性碎片,对应的预解离时间常数分别约为4和3ps.碎片离子的产生有两个途径,分别来自于母体离子的解离和基态高振动态势能面上中性碎片的电离.     

分子动力学模拟纳米尺寸限制体系下氩溶液中I2的振动能量弛豫

利用平衡态分子动力学方法(EMD)模拟了纳米尺寸限制球壳内I2在Ar溶液中的振动能量转移. 计算并讨论了I2振动能量弛豫时间T1随球壳半径、溶剂密度的变化规律. 通过分子间相互作用分析, 在原子、分子水平上, 揭示了随着球壳半径的减小, T1呈逐渐增大趋势的原因. 结果表明, 球壳的几何限制效应和表面作用对受限溶液密度分布的影响较大, 从而导致溶质振动弛豫的显著变化. 此外, 非限制体系模拟显示, 非平衡态分子动力学(NEMD)方法可以得到与平衡态分子动力学方法较一致的振动能量弛豫时间T1.     

Hydration Dynamics of Water near an Amphiphilic Model Peptide at Low Hydration Levels: A Dielectric Relaxation Study

A dielectric relaxation study of aqueous solutions of the amphiphilic model peptide N‐acetyl‐leucine amide (NALA) at 298 K over a wide range of hydration levels is presented. The experiments range from states where water builds up several hydration layers to states where single water molecules or small water clusters are shared by several NALA molecules. The dielectric spectra reveal two modes on the 10 and 100 ps timescales. These are largely broadened with regard to the Lorentzian shape caused by simple Debye‐type relaxation, and are well described by the Kohlrausch–Williams–Watts stretched exponential function. The fast mode is assigned to water reorientation comprising bulk water as well as hydration water. Even when all water molecules are in contact with the solute, this fast component is dominant, and its mean relaxation time is retarded by less than a factor of two relative to neat water. The amplitude of the slow process is far higher than expected for the dipolar reorientation of the solute. The observations are consistent with results from molecular dynamics simulations for a similar model peptide reported in the literature. They suggest that the slow relaxation mode is mainly founded in peptide–water dipolar couplings, with some additional contribution from slowly reorienting hydration water molecules. The results are discussed with regard to the hydration dynamics of proteins and the interpretation of dielectric spectra of protein solutions.     

Hydration and dynamic behavior of cyclodextrins in aqueous solution

The hydration state and dynamics of plain and chemically modified cyclodextrins (CDs) in aqueous solution were investigated by using dielectric relaxation measurements at 25 degrees C over a wide frequency range up to 20 GHz, which is the relaxation frequency of pure liquid water molecules. The obtained dielectric relaxation spectra were decomposed into two major and one minor relaxation modes with relaxation times of approximately 8.3, 20-25, and 1000-2500 ps, respectively, depending on the CD species. The two major modes, fast and medium, were attributed to a rotational relaxation process of water molecules belonging to the bulk (free) state and an exchange of water molecules hydrated to CDs owing to hydrogen bond formation. The hydration numbers of the CDs strongly depend on the number of hydroxy (OH) groups controlled by chemical modification such as methylation. Increasing the number of methoxy or 2-hydroxypropoxy groups increases the hydration number of CD molecules, and results in higher solubilities of the chemically modified CDs than those of the plain CDs. The minor, slow mode was assigned to overall rotational relaxation for CDs with finite permanent dipole moments, which also depends on the number of OH groups.     

Multidimensional infrared spectroscopy of the N-H bond motions in formamide

The heterodyned two-dimensional (2D) IR spectra and equilibrium dynamics of the N-H stretching motion of DCONHD in deuterated formamide, DCOND(2), were studied with 80 fs pulses at 3 microm. The time evolution of the heterodyned 2D IR spectra, pump-probe spectra, and photon echo peak shift demonstrate that interstate dynamics is occurring by relaxation of the original N-H excitation. The N-H vibrational frequency correlation function can be expressed as a sum of three exponentials with correlation times 0.24 ps, 0.8 ps, and 11 ps. The intermediate component is attributed to motions of the N-Hcdots, three dots, centeredO unit involving only slight angular variations of the N-H bond. The slow component is attributed to the structure breaking and making. The anisotropy decay confirmed that the significant angular N-H bond motion occurs on the 11 ps time scale. The fast component, which is the least well determined, might correspond to the modulation of the H-bond distance without angular motion. The correlation coefficient between the pumped and relaxed state distributions was +0.51, implying that the excited state phase memory is only slightly diminished by the relaxation of the N-H excitation. The relaxed modes are concluded to be local to the driven N-H mode.     

Dimeric molecular association of dimethyl sulfoxide in solutions of nonpolar liquids

Although many vibrational spectroscopic studies using infrared (IR) absorption and Raman scattering (RS) techniques revealed that dimethyl sulfoxide (DMSO) forms intermolecular dimeric associations in the pure liquid state and in solutions, the results of a number of dielectric relaxation studies did not clearly show the presence of such dimers. Recently, we found the presence of dimeric DMSO associations in not only the pure liquid but also in solutions of nonpolar solvents, such as tetrachloromethane (CCl(4)) and benzene (Bz), using dielectric relaxation (DR) techniques, which ranged from 50 MHz to 50 GHz at 25 °C. The dimeric DMSO associations cause a slow dielectric relaxation process with a relaxation time of ca. 23 ps for solutions in CCl(4) (ca. 17 ps in Bz) due to the dissociation into monomeric DMSO molecules, while the other fast relaxation is caused by monomeric DMSO molecules with a relaxation time of ca. 5.0 ps (ca. 5.5 ps in Bz) at 25 °C. A comparison of DR and vibrational spectroscopic data for DMSO solutions demonstrated that the concentration dependence of the relative magnitude of the slow and fast DR strength corresponds well to the two IR and RS bands assigned to the vibrational stretching modes of the sulfoxide groups (S═O) of the dimeric associations and the monomeric DMSO molecules, respectively. Moreover, the concentrations of the dimeric associations ([DIM]) and monomeric DMSO molecules ([MON]) were governed by a chemical equilibrium and an equilibrium constant (K(d) = [DIM](2)[MON](-1)) that was markedly dependent on the concentration of DMSO and the solvent species (K(d) = 2.5 ± 0.5 M(-1) and 0.7 ± 0.1 M(-1) in dilute CCl(4) and Bz solutions, respectively, and dramatically increased to 20-40 M(-1) in pure DMSO at 25 °C).     

Dielectric response of imidazolium-based room-temperature ionic liquids

We have used microwave dielectric relaxation spectroscopy to study the picosecond dynamics of five low-viscosity, highly conductive room temperature ionic liquids based on 1-alkyl-3-methylimidazolium cations paired with the bis((trifluoromethyl)sulfonyl)imide anion. Up to 20 GHz the dielectric response is bimodal. The longest relaxation component at the time scale of several 100 ps reveals strongly nonexponential dynamics and correlates with the viscosity in a manner consistent with hydrodynamic predictions for the diffusive reorientation of dipolar ions. Methyl substitution at the C2 position destroys this correlation. The time constants of the weak second process at the 20 ps time scale are practically the same for each salt. This intermediate process seems to correlate with similar modes in optical Kerr effect spectra, but its physical origin is unclear. The missing high-frequency portion of the spectra indicates relaxation beyond the upper cutoff frequency of 20 GHz, presumably due to subpicosecond translational and librational displacements of ions in the cage of their counterions. There is no evidence for orientational relaxation of long-lived ion pairs.     

Dielectric relaxation behavior of aqueous solutions of carbobetaines with varying intercharge distances

The dielectric relaxation behavior of aqueous triethylammonioalkanoate (carbobetaine: Et(3)nCB) solutions was examined as a function of frequency from 1.00 x 10(6) to 2.00 x 10(10) Hz (6.28 x 10(6) to 1.26 x 10(11) rad s(-1) in angular frequency); number of intercharge methylene groups, n = 1, 3, 4, 5, and 10; and solute concentration, c. Two major relaxation modes, fast and slow, were found in all solutions examined. Et(3)nCB systems with n = 5 and 10 possessed another, medium, relaxation mode with relaxation time tau(Dh) at high c values (above the contact concentration of solutes) in addition to the fast and slow modes. The fast mode with a relaxation time, tau(w), of approximately 10 ps was attributed to the rotational motion of bulk water molecules. The slow mode with a relaxation time, tau, of 0.08-1 ns, depending on the n value, was attributed to the overall rotational motion of each carbobetaine in aqueous solution. The concentration normalized relaxation strength, Deltaepsilonc(-1), and tau value of the slow relaxation mode increased with increasing n. These findings were quantitatively explained on the basis of changes in the intercharge distance resulting in increased size and dipole moment of the carbobetaines. Above the contact concentration, collisions between solute molecules likely hindered their rotational motions, leading to an increase in tau. The middle relaxation mode found in longer Et(3)nCBs (n = 5 and 10) with a relaxation time, tau(Dh), of approximately 0.2 ns, more than 20 times as long as that of bulk water molecules, tau(w), was attributed to the dehydration of water molecules tightly bound to all Et(3)nCBs examined (including those with n < 5). This mode was not observed in the solutions of Et(3)nCBs with n < 5, since the tau values corresponding to overall rotation were close to or shorter than the tau(Dh) values.     

Reconsideration of the anomalous dielectric behavior of dimethyl sulfoxide in the pure liquid state

Although many vibrational spectroscopic studies using infrared absorption and Raman scattering techniques reveal that dimethyl sulfoxide (DMSO) forms intermolecular associations, such as dimers, in the pure liquid state, the results of many dielectric relaxation studies deny the presence of such associations and claim very little orientational correlation between the dipoles of DMSO molecules because of a Kirkwood correlation factor close to unity in the pure liquid state and in solution. Recently, we found reasons for the inconsistency and elucidated the presence of dimeric DMSO associations via dielectric relaxation measurements from 50 MHz to 50 GHz. The dissociation of DMSO dimers is the major dielectric relaxation process with a relaxation time of 19 ps, while the relaxation of monomeric DMSO is a minor mode with a relaxation time of 4.5 ps at 25 °C and slightly increasing strength with increasing temperature.     

Spatial regimes in the dynamics of polyolefins: collective motion

Molecular simulation is used to characterize the spatial dependence of collective motion in four saturated hydrocarbon polymers. The observable is the distinct intermediate scattering function, as measured in coherent quasielastic neutron scattering experiments. Ranges of 0.01-1000 ps in time and 2-14 A in spatial scale are covered. In this time range, a two-step relaxation, consisting of a fast exponential decay and a slower stretched decay, is observed for all spatial scales. The relaxation times for the fast process are very similar to those obtained by following self motion, with a small modulation of relaxation times near the peak in the static structure factor which is well described by the narrowing picture suggested by de Gennes. For the slow process, self and collective relaxation times have larger numerical differences and follow different scaling with spatial scale. The modulation of slow relaxation times is larger than that observed for the fast process, but is overestimated by the de Gennes prediction, which only works qualitatively.     

Influence of pressure on the slow and fast fractional relaxation dynamics in lysozyme: a simulation study

The article reports on a molecular dynamics simulation study of the influence of moderate, nondenaturing pressure on the slow and fast internal relaxation dynamics of lysozyme. The model parameters of the fractional Ornstein-Uhlenbeck process are used to quantify the changes. We find that the nonexponential character for diffusive motions on time scales above 10 ps is enhanced and that the diffusion processes are slowed down. The diffusive motions on the subpicosecond time scale appear, in contrast, accelerated, whereas the nonexponential character is not altered by pressure. We attribute these findings to the different natures of slow and fast relaxation processes, which are characterized by structural rearrangements and collisions, respectively. The analyses are facilitated by the use of spatially resolved relaxation rate spectra.     

Intra- and inter-monomeric transfers in the light harvesting LHCII complex: the Redfield-Förster picture

We further develop the model of energy transfer in the LHCII trimer based on a quantitative fit of the linear spectra (including absorption (OD), linear dichroism (LD), circular dichroism (CD), and fluorescence (FL)) and transient absorption (TA) kinetics upon 650 nm and 662 nm excitation. The spectral shapes and relaxation/migration rates have been calculated using the combined Redfield-F?rster approach capable of correctly describing fast relaxation within strongly coupled chlorophyll (Chl) a and b clusters and slow migration between them. Within each monomeric subunit of the trimeric complex there is fast (sub-ps) conversion from Chl's b to Chl's a at the stromal side accompanied by slow (>10 ps) equilibration between the stromal- and lumenal-side Chl a clusters in combination with slow (>13 ps) population of Chl's a from the 'bottleneck' Chl a604 site. The connection between monomeric subunits is determined by exciton coupling between the stromal-side Chl's b from the two adjacent subunits (Chl b601'-608-609 cluster) making a simultaneous fast (sub-ps) population of the Chl's a possible from both subunits. Final equilibration occurs via slow (>20 ps) migration between the Chl a clusters located on different monomeric subunits. This migration includes up-hill transfers from the red-most Chl a610-611-612 clusters located at the peripheral side in each subunit to the Chl a602-603 dimers located at the inner side of the trimeric LHCII complex.