聚酰胺66溶液弛豫行为的NMR研究

用1D和2D NMR技术归属了聚酰胺66的1H和13C的NMR共振信号,并通过聚酰胺66溶液温度和浓度改变对氢核弛豫时间的影响,得到了其分子运动信息.结果表明随着温度的升高,聚酰胺66链间氢键逐渐解离,大分子链间相互作用逐渐减弱.而解离出来的链段又与溶剂小分子可以形成新的氢键,使聚酰胺66链卷曲并包含着部分溶剂分子一起运动.随着溶液浓度的增大,由于分子链间距变小,使得分子间作用力增强,链缠结程度加大,使链运动受限.     

基于缠结微结构的非晶态玻璃态高分子材料屈服行为的分子动力学研究

非晶态玻璃态高分子材料作为结构材料在工程领域应用广泛,其机械力学性能特别是屈服变形行为受到热处理、加载应变率和环境温度的影响.采用分子动力学模拟方法研究非晶态玻璃态高分子材料不同工况下的单轴拉伸变形,基于分子链缠结微结构的概念,阐明了非晶态玻璃态高分子材料屈服和应变软化过程的内在变形机制.结果表明,拓扑缠结具有较为稳定的空间结构,难以发生解缠,决定了非晶态高分子材料屈服后的软化平台.由相邻分子链的局部链段相互作用形成的次级缠结在一定外界条件下可发生破坏或重新生成,次级缠结微结构及其演化是非晶态高分子材料发生屈服及软化的内在物理原因.     

链构象对稀溶液中MEH-PPV的光致发光的影响

聚(2-甲氧基-5-(2’-乙基己氧基)-1,4-对苯乙炔)(MEH-PPV)在溶液中的链构象依赖于溶剂的性质,共轭聚合物的发光特性受链构象影响明显。在稀溶液中,不良溶剂含量的增加使MEH-PPV分子链更加紧缩卷曲,单个分子链内更多共轭链段发生聚集,光激发形成的链间激子增加。通过对MEH-PPV稀溶液的光谱分析,发现链间激子的形成过程依赖于激发光的能量(hv)。在激发光能量大于聚合物的最低激发能(E4)的情况下,大部分链内激子通过辐射复合发光,少部分链内激子沿分子链转移到聚集的共轭链段上形成链间激子。在hv＜Ea的情况下,单个分子链内聚集共轭链段吸收光子能量形成链问激子并复合发光。     

~1H NMR研究β—环糊精与环氧氯丙烷共聚物的反应机理和分子链结构

β-环糊精(cyclodcxtrin)与环氧氯丙烷(Epichlorohydrin)一个系列的共聚物获得,~1HNMR以D_2O或DMSO-d_6为溶剂的测定,其谱峰被归属.共聚合反应机理为以羟基和环氧基为活性中心的亲核取代.当环氧氯丙烷:β-环糊精=n≤3时,聚合物分子链呈现以β-环糊精母体为中心的线状或低枝化状链结构;当n≥5时,分子链出现交联网络结构.n越大(n≤12),分子量越急剧增加,其交联度也越大.     

多环芳烃在超临界环己烷中的溶解：分子动力学模拟研究

重油中大量存在的多环芳烃会经过缩合反应会形成稠环芳烃，而溶解扩散的限制会导致稠环芳烃之间的聚合从形成残焦，使得对重油的利用率大大降低，所以多环芳烃热解过程的溶解扩散是重油改质的关键因素之一.因此，基于环己烷对烃类良好的溶解性，本文采用分子动力学模拟的方法研究了多环芳烃及其混合物在超临界环己烷中的溶解行为，结果表明在不同温度与密度下超临界环己烷对于具有NAP均具有良好的溶解性，而温度对于Bghip溶解的影响较小.在多环芳烃混合物的油滴溶解过程中，NAP优先溶解到环己烷相中，而Bghip则集中在粒径减小的油滴中.通过计算体系中多环芳烃的径向分配函数与溶剂化自由能发现环己烷与多环芳烃间之间能相互吸引，环己烷在多环芳烃分子周围形成的溶剂壳能抑制多环芳烃分子间的聚合.温度升高以及密度的将降低会导致多环芳烃的内聚能密度降低，增加了多环芳烃与超临界环己烷之间的相互作用.环己烷密度越小以及温度的升高可以促进多环芳烃或多环芳烃混合物在超临界环己烷中的溶解.     

1H NMR研究β-环糊精与环氧氯丙烷共聚物的反应机理和分子链结构

β-环糊精(cyclodcxtrin)与环氧氯丙烷(Epichlorohydrin)一个系列的共聚物获得,¹H NMR以D₂O或DMSO-d₆为溶剂的测定,其谱峰被归属.共聚合反应机理为以羟基和环氧基为活性中心的亲核取代.当环氧氯丙烷:β-环糊精=n ≤ 3时,聚合物分子链呈现以β-环糊精母体为中心的线状或低枝化状链结构;当n ≥ 5时,分子链出现交联网络结构.n越大(n ≤ 12),分子量越急剧增加,其交联度也越大.     

激子旋转弛豫对低掺杂卟啉侧链聚合物荧光衰变过程的影响

利用激子旋转扩散理论研究了一类低掺杂卟啉侧链聚合物中卟啉侧链基团的旋转对其发光动力学过程的影响.研究表明,卟啉侧链基团的旋转行为是导致激发态无辐射能量弛豫的重要途径.基团旋转越容易,能量弛豫速度越快,这可导致一个快速的荧光衰变动力学过程.在卟啉低掺杂浓度和聚合物分子链间距离较大的情况下,卟啉侧链基团的旋转成为影响荧光寿命和发光效率的主要因素.对实验测得的两种样品的荧光弛豫过程进行了拟合,理论结果与实验结果符合较好. 关键词： 激子旋转弛豫 瞬态荧光 卟啉侧链聚合物     

用NMR弛豫研究溶液中聚苯乙烯的缠结特性

详细研究了在θ溶剂环已烷和二氧六环中聚苯乙烯(PS)链的弛豫特性随分子量、浓度和温度的变化规律,发现在PS的溶液中同时存在拓扑缠结和凝聚缠结.前者的形成强烈的依赖于分子量、浓度和温度,而后者主要同浓度和温度有关.侧基苯环的层叠作用(即凝聚缠结)对PS的溶解过程及主链的运动有很大影响,从而对PS的溶液性质乃至固体性质起着决定性作用.另外还发现在不同分子量范围内,分子量对PS的弛豫特性的影响明显不同.这被解释为同溶液中PS链的缠结的形成,单位体积内缠结点数的增加等因素有关.     

PET与SAN/PAN复合膜界面的 FTIR-ATR研究

应用傅里叶衰减全反射红外光谱(FTIR-ATR)技术对聚对苯二甲酸乙二酯(PET)表面形成不同厚度的超薄苯乙烯-丙烯腈共聚物(SAN)和聚丙烯腈(PAN)的共混物膜及其SAN/PAN共混物膜的厚度、界面层PET亚甲基的构像变化等进行研究,结果表明PET表面共混物膜的厚度随共混物混合液中SAN含量的增加而增加,界面层成膜物质与基材的分子链段间发生了相互渗透和扩散,分子链的极性越相近,越容易成膜.对PET红外光谱吸收峰的A1340/A1410进行定量研究表明,在成膜过程中,PET分子链的亚甲基构像由反式向旁式转变,引起界面层PET的结晶度降低.FTIR-ATR是分析复合膜界面层结构信息的有效方法.     

用NMR弛豫研究溶液中聚苯乙烯的缠结特性

详细研究了在θ溶剂环已烷和二氧六环中聚苯乙烯（ＰＳ）链的弛豫特性随分子量、浓度和温度的变化规律，发现在ＰＳ的溶液中同时存在拓扑缠结和凝聚缠结．前者的形成强烈的依赖于分子量、浓度和温度，而后者主要同浓度和温度有关．侧基苯环的层叠作用（即凝聚缠结）对ＰＳ的溶解过程及主链的运动有很大影响，从而对ＰＳ的溶液性质乃至固体性质起着决定性作用．另外还发现在不同分子量范围内，分子量对ＰＳ的弛豫特性的影响明显不同．这被解释为同溶液中ＰＳ链的缠结的形成，单位体积内缠结点数的增加等因素有关．     

Temperature-Induced Swelling of Alkali Metal Polyacrylate Gels in Aqueous Organic Solvent Mixtures

It has been known that some polyelectrolyte systems, e.g., betaine polymer and polycations, have an upper critical solution temperature (UCST) in water while polyanions seldom show such a temperature-dependent phase separation. Recently we have found a significant counterion- and solvent-specific UCST-type behavior for alkali metal poly(acrylate)s (PAAM) in aqueous organic solvent mixtures. Namely, the reduced viscosity significantly increased with increasing temperature which was ascribed to disintegration of the ion-clusters or the aggregated ion-pairs formed at the lower temperature. In the present study, we prepared PAAM gel samples by irradiating the aqueous solutions with γ-rays in variable doses to find that a significant gel swelling was induced by a temperature jump from 5 to 40°C in various kinds of aqueous organic solvent mixtures. The UCST-type behavior and the counterion- and solvent-specificities for the gel swelling turned out to be parallel to those for the corresponding solution systems. In addition to these expected results, an appreciable LCST-type deswelling was unexpectedly observed for collapsed gels in a relatively higher solvent concentration region. Further, the γ-ray doses, i.e., the degree of crosslinking, proved to affect the UCST behavior; the gel swelling ratio was more significant for gels prepared with higher doses.     

Improving the gel properties of salted egg white/cooked soybean protein isolate composite gels by ultrasound treatment: Study on the gelling properties and structure

In this study, the effects of ultrasound treatment on the texture, physicochemical properties and protein structure of composite gels prepared by salted egg white (SEW) and cooked soybean protein isolate (CSPI) at different ratios were investigated. With the increased SEW addition, the ζ-potential absolute values, soluble protein content, surface hydrophobicity and swelling ratio of composite gels showed overall declining trends (P < 0.05), while the free sulfhydryl (SH) contents and hardness of exhibited overall increasing trends (P < 0.05). Microstructural results revealed that composite gels exhibited denser structure with the increased SEW addition. After ultrasound treatment, the particle size of composite protein solutions significantly decreased (P < 0.05), and the free SH contents of ultrasound-treated composite gels were lower than that of untreated composite gels. Moreover, ultrasound treatment enhanced the hardness of composite gels, and promoted the conversion of free water into non-flowable water. However, when ultrasonic power exceeded 150 W, the hardness of composite gels could not be further enhanced. FTIR results indicated that ultrasound treatment facilitated the composite protein aggregates to form a more stable gel structure. The improvement of ultrasound treatment on the properties of composite gels was mainly by promoting the dissociation of protein aggregates, and the dissociated protein particles further interacted to form denser aggregates through disulfide bond, thus facilitating the crosslinking and reaggregation of protein aggregates to form denser gel structure. Overall, ultrasound treatment is an effective approach to improve the properties of SEW-CSPI composite gels, which can improve the potential utilization of SEW and SPI in food processing.     

Entanglement routers using macroscopic singlets

We propose a mechanism where high entanglement between very distant boundary spins is generated by suddenly connecting two long Kondo spin chains. We show that this procedure provides an efficient way to route entanglement between multiple distant sites. We observe that the key features of the entanglement dynamics of the composite spin chain are well described by a simple model of two singlets, each formed by two spins. The proposed routing mechanism is a footprint of the emergence of a Kondo cloud in a Kondo system and can be engineered and observed in varied physical settings.     

Tuning the optical properties of Fe-Au core-shell nanoparticles with spherical and spheroidal nanostructures

Present research interest is to highlight on the manufacturing of core-shell nanoparticles because of core activity with unique properties and surface modification by a shell in the diverse fields (e.g. optoelectronic, catalysis and magneto-optics). In addition, the combined optical properties of magnetic-plasmonic core-shell NPs make them ideal candidates for many applications in biomedical fields. The influence of Fe-core and Au-shell for the formation of the core-shell viz. spherical and spheroidal nanostructures is studied using the discrete dipole approximation method. DDA is an approximation method and its accuracy is compared to Mie theory results for spherical core-shell NPs as Mie theory gives the exact solution to spherical targeted NPs. DDA calculations are further extended to spheroidal core-shell nanostructures. It is observed that the localized surface plasmon resonance (LSPR) peak position in considered core-shell nanostructures is enhanced by changing the cores and shell thickness in the core-shell spherical nanostructures and aspect ratio as well as shell thickness in spheroidal core-shell nanostructures. The absorption spectra are found between 363–788 nm wavelength ranges and can be tuned into UV-visible-near-infrared region of the electromagnetic (EM) spectrum in accordance with desired applications. It has been found that the Fe@hollow@Au and prolate core-shell nanostructures show enhancement to LSPR peaks, bandwidth and their corresponding intensities in comparison to other considered spherical and spheroidal core-shell nanostructures. Tunability in core size, shell thickness, aspect ratio, and configuration will open new potential uses of suitable magnetic-plasmonic core-shell nanostructures in cancer therapy, tissue engineering, drug delivery, and many more of biomedical fields.     

芯-壳结构复合纳米颗粒

芯－壳结构复合纳米颗粒因其独特结构而具有许多奇异的性质，尤其体现在可人工设计和可控的光学性质上：根据不同的性质要求，通过改变组分和壳层与芯部的相对尺寸来实现光学性质在很宽波段范围内的可调特性，这一特性在光敏器件（如光开关，光过滤器）以及下一代的纳米光子光等很多领域有着广阔的应用前景，并在目前红外材料的改性上也会大显身手，文章介绍了几种芯－壳复合纳米颗粒的合成及其性质研究现状，并作相应的展望。     

Generation of rectangular prismatic dislocation loops in shells and cores of composite nanoparticles

A theoretical model has been proposed for describing the relaxation of misfit stresses in a spherically symmetric composite core-shell nanoparticle due to the generation and expansion of rectangular prismatic dislocation loops at the internal and external interfaces. The critical conditions of the formation of these loops have been calculated for nanoparticles consisting of a relatively massive core and a thin shell. It has been shown that the generation of dislocation loops is possible when the misfit of the lattice parameters of the core and shell of the nanoparticle exceeds a critical value that depends on the nanoparticle radius, the shell thickness, the loop formation position, and the shape of loops. This condition holds for a loop in the shell when the shell thickness either lies in a specific range of small values or (for a larger misfit) is less than a critical value. For the generation of loops in the core, the shell thickness should exceed a critical value. The dislocation loops elongated along the core-shell interface are formed more readily. As the shell thickness increases at a fixed nanoparticle radius, the energetically more favorable generation of a dislocation loop occurs first from the free surface into the bulk of the shell, then from the interface into the shell, and finally from the interface into the core of the nanoparticle.     

Influence of environmental solution pH and microstructural parameters on mechanical behavior of amphoteric pH-sensitive hydrogels

Amphoteric hydrogels contain both ionizable acidic and basic groups attached on the polymer chains, which can change their volume in response to the slight alteration of the surrounding environmental p H. In this paper, a theory of equilibrium swelling of amphoteric p H-sensitive hydrogels which is an extension of the formalism proposed by Marcombe et al. and a new hybrid free-energy density function of amphoteric hydrogels composed of the Edwards-Vilgis slip-link model and the Flory-Huggins solution theory as well as the contributions of mixing the mobile ions with the solvent, and dissociating the acidic and basic groups are presented for the prediction of the influence of environmental solution p H, microstructural parameters and geometric constraints on mechanical behavior. The calculations were modeled on chitosan-genipin gels, and the results were compared to experimental data. Numerical calculations show that the model is able to predict the dependence of swelling on p H and crosslinker qualitatively well and quantitatively close to the experimental data. Each gel shows minimal swelling at low p H but an increase in swelling until a maximum was reached; for most of the p H range, a good fit was achieved except for where the maximum swelling occurs; for experimental data, the maximum swelling appears at about pH = 4 , but for modeled data the maximum swelling appears between pH = 4 and pH = 6 ; each gel swell decreasing with increasing crosslinker concentration was also successfully predicted. The calculated results also show that microstructural parameters and geometric constraints have a significant impact on the mechanical behavior of the amphoteric hydrogels; the gel swells less when the network is more densely entangled and the maximum swelling ratio of the gels under biaxial constraint is only about one-third of the maximum when the gels swell freely. The theory developed here is valuable for the design and optimization of a drug delivery system.     

GdF_3∶Ce~(3+),Dy~(3+)@GdF_3∶Eu~(3+)核壳结构荧光粉溶剂热法制备及其多色发光性能研究

采用溶剂热法合成了核壳结构纳米荧光粉GdF_3∶Ce~(3+),Dy~(3+)@GdF_3∶Eu~(3+)。XRD衍射图样显示所制备纳米晶为正交相;在Ce~(3+)的8S7/2→6IJ激发峰激发下,该核壳结构具有明显的多色发光性能,而在相应的非核壳结构中却由于Ce~(3+)共掺导致Eu~(3+)出现荧光猝灭现象。基于CIE坐标,可以看出该体系的核壳结构具有比非核壳结构优越的发光性能,这主要是因为Gd~(3+)起到媒介离子的作用。最后,讨论了壳厚度对发光的影响,结果发现当核壳的量比为1∶3时,荧光粉具有最大的发光强度。     

Entanglement dynamics of three-qubit coupled to an XY spin chain at finite temperature with three-site interaction

The entanglement dynamics of three-qubit states under an XY spin chain at finite temperature with three-site interaction is investigated. It is shown that the three-site interaction does not affect the behavior of quantum phase transition (QPT) induced by the external magnetic field and does not induce new critical regions in the XY model. In addition, concerned with the effect of the three-site interaction on the entanglement evolution, we find the three-site interaction can not only enhance but also suppress the decay of the entanglement between the three-qubit system, which depends on the initial states of the system and the parameters related with the environmental spin chain.     

受限壁的选择性对软受限下星形三嵌段共聚物形貌的影响

基于嵌段共聚物在软受限条件下能够自组装形成很多有序结构,在催化、电子器件、光学传感等领域有广泛的应用价值,目前只对线性三嵌段共聚物在软受限下的自组装形貌做了分析,对星形三嵌段共聚物在软受限下的自组装行为还未有一个统一的定论.在这项研究中,应用模拟退火来研究ABC星形三嵌段共聚物在软受限下的自组装行为,嵌段与溶剂没有选择性下(中性壁),通过调整三个嵌段(f_A、f_B和f_C)的体积分数来构建相图,我们的模拟预测了各种独特的自组装纳米结构,包括薄片+球形、圆柱状,穿孔层,薄片+圆柱体,核壳补丁.然后通过改变嵌段与溶剂的选择性预测了链长度比为1:x:1的共聚物粒子形貌.通过计算接触数、均方根末端距与平均链长的比值以及平均键长随x的变化,验证了形貌转变机制.