利用微悬臂梁表面应力研究聚N-异丙基丙烯酰胺分子的构象转变

提出了一种基于微悬臂梁传感技术研究大分子折叠/构象转变的新方法.通过分子自组装的方法将热敏性的聚N-异丙基丙烯酰胺(PNIPAM)分子链修饰到微悬臂梁的单侧表面,用光杠杆技术检测温度在20-40 ℃之间变化时由于微悬臂梁上的PNIPAM分子在水中的构象转变所引起的微悬臂梁变形.实验结果显示:在升温过程中,微悬臂梁的表面应力发生了变化并且导致微悬臂梁产生了弯曲变形,这个过程对应着微悬臂梁上的PNIPAM分子从无规线团构象到塌缩小球构象的构象转变.在降温过程中,微悬臂梁发生了反方向的弯曲变形,这对应着PNIPAM分子从塌缩小球构象向无规线团构象的构象转变.整个温度变化过程中构象转变是连续进行的,而在低临界溶解温度(约32 ℃)附近转变幅度较大,这与自由水溶液中PNIPAM分子的无规线团-塌缩小球构象转变相对应.实验结果还显示:由于PNIPAM分子在塌缩过程中氢键的形成和链段间可能的缠结效应,整个温度循环过程中微悬臂梁的变形是不可逆的且有明显的迟滞效应.     

利用微悬臂梁研究聚N-异丙基丙烯酰胺在金表面的自组装

利用微悬臂梁传感技术研究了巯基化的聚N-异丙基丙烯酰胺（HS-PNIPAM）在微悬臂梁金面上的自组装过程.由于大分子的构象变化改变了分子间的相互作用,导致微悬臂梁的表面应力改变,使微悬臂梁发生弯曲.通过光学方法实时读出微悬臂梁的弯曲信号,得到HS-PNIPAM的自组装动力学曲线.通过对不同分子量HS-PNIPAM的实验结果分析表明：HS-PNIPAM在自组装过程中存在三个阶段,分别对应不同的分子构象.第一阶段为物理吸附阶段,第二、三阶段为伴随着分子构象变化的化学吸附阶段.吸附曲线符合Langmuir等温吸附.分析结果还显示HS-PNIPAM的表面吸附速率κ远小于小分子的吸附速率,并与分子量成负指数关系;HS-PNIPAM的自组装时间远大于小分子的自组装时间,并与分子量成正比;底物表面应力的改变与HS-PNIPAM的分子量成线性关系. 关键词： 微悬臂梁 聚N-异丙基丙烯酰胺 自组装 构象转变     

N-异丙基丙烯酰胺水凝胶的红外光谱

合成了聚N-异丙基丙烯酰胺(poly(N-isopropylacrylamide,PNIPAM),并利用傅立叶变换红外光谱方法,对N-异丙基丙烯酰胺及其聚态在溶液相的构象进行了表征。发现在异丙醇中N-异丙基丙烯酰胺单体结构并不存在,而是以二聚体的形式存在。而所形成的PNIPAM聚集体,其酰胺基团的典型光谱峰-酰胺-Ⅰ带的红外光谱具有无规则卷曲的特征。这些工作,在理解特异化学基团在PNIPAM中引入后的结构,在原位表征PNIPAM水凝胶体系的动态功能结构等方面打下了基础。     

PNIPAM线性链与凝胶在二元溶剂中相变的变温NMR研究

通过对聚N-异丙基丙烯酰胺（PNIPAM）水溶液和凝胶在水和甲醇混合溶剂中的¹H NMR谱图以及弛豫时间(T₁与T₂)等多种NMR参数随温度变化的研究,发现PNIPAM大分子的基团质子NMR信号、溶剂的弛豫时间都可以用来灵敏表征PNIPAM在二元溶剂中的相变行为. 在PNIPAM凝胶中,温度升到LSCT以上,溶剂峰由单峰变为双峰,分别对应于受限在大分子网络内的受限溶剂和排除到大分子网络外的自由溶剂,两者的弛豫时间存在明显差异. 在PNIPAM溶液中,溶剂峰在相变前后并没有显著变化. 通过PNIPAM溶胀在water/alcohol混合溶剂中的相变研究进一步证实了PNIPAM与不同溶剂之间的相互作用强弱.      

荧光标记的聚(N-异丙基丙烯酰胺)链在水溶液中的折叠动力学

使用1.54 μm的激光脉冲(脉宽约10 ns)诱导丹磺酰基标记的热敏性线性聚N-异丙基丙烯酰胺(PNIPAM)发生线团到小球的转变．当聚合物链中NIPAM单体与丹磺酰基基团的摩尔比由110增至300时,共价键合到聚合物主链上的丹磺酰基发色团对PNIPAM相转变行为的影响会随之减小．PNIPAM链塌缩经历成核过程(伴随着初始珍珠的形成,快弛豫时间τ_fast=0.1 ms)和珍珠的增长粗化阶段(慢弛豫时间τ_slow=0.5 ms),这与之前使用水溶性的1-苯胺-8-萘磺酸铵盐作为荧光探针研究PNIPAM在水溶液中的折叠动力学得到的结果类似．τ_fast在很宽的分子量范围内都与分子量无关,而τ_slow则随链长增加而略有增大．     

两末端染料修饰PNIPAM链的折叠动力学研究（英文）

本文通过原子转移自由基聚合方法合成了两种窄分布的聚(N-异丙基丙烯酰胺)(PNIPAM).用一种新型的含丹磺酰基(dansyl)的化合物作为引发剂,从而使PNIPAM一末端带有丹磺酰基荧光基团.PNIPAM的另一末端通过点击化学连接dabcyl基团.稳态荧光实验发现当PNIPAM溶液温度从36℃升至45℃时,丹磺酰基荧光强度以及dansyl与dabcyl之间的能量转移效率随温度的升高而增加,说明升温过程中dansyl周围的微环境变得疏水,且dansyl与dabcyl之间的距离逐渐缩短.利用自主搭建的激光诱导温度跃变结合荧光检测装置,研究了两末端修饰染料的PNIPAM的折叠动力学.结果表明,对聚合度为85和142的PNIPAM而言,其dansyl荧光强度变化的特征时间分别为3.8 ms和5.8 ms,说明特征时间与链的长度相关.此外,聚合度为85的PNIPAM的能量转移变化的特征时间为2.9 ms,说明能量转移的变化要快于dansyl的荧光强度变化.     

DTPA—PNIPAAm的合成及热敏性实验

水溶性高分子近年来引起了科学界的广泛关注，己广泛用在药物合成、作血浆替代物和药物输运载体。自1968年Heskins发现聚N-异丙基丙烯酰胺（PNIPAAm）水溶液具有最低临界溶液温度的特性以来，热敏高分子成为国际上的研究热点之一。基于聚N-异丙基丙烯酰胺和聚N-异丙基甲基丙烯酰胺的热敏高分子因其独特的温度敏感性还可应用于控制释放、酶的固化、循环吸收和免疫分析等领域，这种高分子的一个显著特点就是有一个固定的较低相转变温度（约30-31℃），在很窄的温度范围内其溶解度会发生显著变化，而且在高温时溶解度降低。     

聚(N-异丙基丙烯酰胺)模板法制备二氧化硅中空微球

以在50 oC水溶液中析出的聚(N-异丙基丙烯酰胺) (PNI-PAM)聚集体作为软模板,使正硅酸乙酯吸附在PNIPAM聚集体表面进行水解缩合,原位生成二氧化硅包裹PNIPAM的核壳结构微球;进一步冷却至室温使PNIPAM溶解在水中除去内核,从而成功合成出SiO₂中空微球．实验表明,只有在足够的PNIPAM和正硅酸乙酯含量以及正硅酸乙酯水解时间下,才能形成稳定的SiO₂中空微球．用TEM、SEM和FTIR对合成的SiO₂中空微球进行了表征,结果表明,微球尺寸为150 nm左右,并且由于PNIPAM上酰胺基团和正硅酸乙酯水解出来的硅醇间具有静电相互作用,使得SiO₂壳层上依然有PNIPAM残留.     

Transitional Process of Ploy(N-isopropylacrylamide) in Deuterated Solution

采用激光诱导温度跃变技术结合纳秒量级时间分辨的中红外吸收差谱的实验方法对聚异丙基丙烯酰胺在重水溶液中的相变过程进行了研究. 首次在实验上观测到位于1570～1700 cm^-1 能量范围内酰胺峰I′的瞬态红外差谱的多峰结构和长链聚异丙基丙烯酰胺分子在相变过程中的多步骤动力学过程.     

两末端染料修饰PNIPAM链的折叠动力学研究

本文通过原子转移自由基聚合方法合成了两种窄分布的聚(N-异丙基丙烯酰胺)(PNIPAM). 用一种新型的含丹磺酰基(dansyl)的化合物作为引发剂,从而使PNIPAM一末端带有丹磺酰基荧光基团. PNIPAM的另一末端通过点击化学连接dabcyl基团. 稳态荧光实验发现当PNIPAM溶液温度从36 °C升至45 °C时,丹磺酰基荧光强度以及dansyl与dabcyl之间的能量转移效率随温度的升高而增加,说明升温过程中dansyl周围的微环境变得疏水,且dansyl与dabcyl之间的距离逐渐缩短. 利用自主搭建的激光诱导温度跃变结合荧光检测装置,研究了两末端修饰染料的PNIPAM的折叠动力学. 结果表明,对聚合度为85和142的PNIPAM而言,其dansyl荧光强度变化的特征时间分别为3.8 ms和5.8 ms,说明特征时间与链的长度相关. 此外,聚合度为85的PNIPAM的能量转移变化的特征时间为2.9 ms,说明能量转移的变化要快于dansyl的荧光强度变化.     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

Phase behavior of DODAB aqueous solution

Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4°C at heating and one transition at the temperature 40.4°C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4°C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.     

Kinetic coefficients of the semiconducting phase of FeSi2 at low temperatures

The results of studying the kinetic coefficients of β-FeSi₂ in the temperature range 4.2–300 K are considered. The resistivity decreases upon heating in the entire temperature range under investigation. The temperature dependences of the resistivity and thermal conductivity exhibit a break at ～20 K. In the range of 4.2–20 K, the resistivity is a linear function of temperature. The thermo-emf increases rapidly upon cooling and attains values exceeding 15 mV/K. The temperature dependence of the thermo-emf exhibits a break at ～40 K. The observed set of temperature dependences of the kinetic coefficients apparently cannot be explained by a superposition of the known effects only. A new effect probably exists that is associated with a strong electron-phonon interaction in FeSi₂ and which requires a further investigation.     

INFLUENCE OF γ-RADIATION ON THE DIELECTRIC CHARACTERISTICS IN Rb2ZnCl4 SINGLE CRYSTALS AT INCOMMENSURATE-COMMENSURATE PHASE TRANSITION

In this paper the influence of γ-radiation on the dielectric constants of Rb₂ZnCl₄ crystal at incommensurate-commensurate phase transition (hereafter abbreviated as INC-C transition) are studied. The thermal hysteresis occurs upon both cooling and heating runs, irrespective of whether the samples have been treated with γ-radiation or not. For the γ-irradiated sample, its transition point, T_c, between the INC and C phases is not changed, but the peak value of the dielectric constant at T_c increases abruptly, compared with that before γ-irradiation, When this sample is annealed at 40℃, the peak value restores to the incipient value for the sample free from γ-irradiation. The origin of the phenomenon of the thermal hysteresis of the dielectric constant may be due to the pinning effect of dejects or impurities in the samples.     

铌酸锂钠在低温时的介电铁电和热电性

在300—20K的温度范围内观测了用丘克拉斯基法生长的Li_0.025Na_0.975NbO₃晶体的介电、铁电和热电特性。介电常数,极化强度和热电性的反常表示该晶体在低温时发生相变。此相变有特别大的热滞(约80K),降温时发生于180K附近,升温时发生于260K附近。测量了晶体的室温结构,指出了可能的低温相点群。观测了热电电荷的时间响应,报道了热电电荷随时间改变符号的特异现象,认为其起因是相变过程中两相共存。 关键词：     

Electrical resistivity of Sn–3.5Ag–xBi solder melts

This article reported the temperature dependence of the electrical resistivity (ρ) of liquid Sn–3.5Ag lead-free solder alloy in continuous heating and cooling processes with varying Bi content in the range of 0, 2, 3.5, 5, and 7?wt.% Abnormal transitions can be observed on ρ–T curves, which indicate liquid–liquid structure transition (LLST) occurs in Sn–3.5Ag–xBi melts. Interestingly, unlike the pattern at first heating cycle, the LLST is reversible during subsequent cooling and heating cycles. Sn may play an important role on the reversibility, and Bi has a noticeable influence on the turning temperatures and characteristics during first heating cycle. The transition mechanism is analyzed from the viewpoint of short-range orders.     

Complex thermal evolution of size-stabilized tetragonal zirconia

Zirconia nanopowder with doping YO_1.5 contents between 0 and 1 mol% were synthesized by the Pechini method. The crystallite dimensions of the powder, around 10 nm, allows for the size stabilization of the tetragonal polymorph over the thermodynamically stable monoclinic one. As the nanopowders are heated to 1200 °C and subsequently cooled back to room temperature, a complex evolution of the phase composition occurs. Upon heating the tetragonal phase transforms slowly into the monoclinic one and the transition cannot be completed before entering the stability range of the tetragonal phase (above 1150 °C). Upon cooling, on the other hand, the reaction is considerably faster and the complete transformation into the monoclinc phase occurs in a narrow temperature range. Rietveld analysis of the high temperature X-ray patterns revealed as, during heating, the transition is mainly controlled by microstructural parameters and in particular it is triggered by the release of RMS microstrain. Upon cooling, on the other hand, the transition is kinetically controlled by the doping content.     

热处理和紫外辐射对DNA影响的拉曼光谱研究

检测了鲕鱼精ＤＮＡ纤维和经过４０℃，９１℃，２００℃加热处理的拉曼光谱。研究结果表明，在熔融温度以下热处理对ＤＮＡ构象的影响是轻微的，在熔融温度以上则随温度的升高，对ＤＮＡ分子结构的影响有破坏也逐渐加剧，首先受影响的是腺嘌呤和脱氧核糖。     

Glass transition in ultrathin polymer films: calorimetric study

The ultrasensitive differential scanning calorimetry is used to observe the glass transition in thin (1-400 nm) spin-cast films of polystyrene, poly (2-vinyl pyridine) and poly (methyl methacrylate) on a platinum surface. A pronounced glass transition is observed even at a thickness as small as 1-3 nm. Using the high heating (20-200 K/ms) and cooling (1-2 K/ms in glass transition region) rates which are typical for this technique, we do not observe appreciable dependence of the glass transition temperature over the thickness range from hundreds of nanometers down to 3 nm thick films. The evolution of calorimetric data with film thickness is discussed in terms of broadening of transition dynamics and loss of transition contrast.     

Deflected light structure in NaNH4SeO4·2H2O crystals

Deflection of light studies in function of temperature in NaNH₄SeO₄·H₂O crystal is presented. At 180?K, this compound undergoes a para-ferroelectric/ferroelastic phase transition of the second order. It changes the symmetry from the orthorhombic symmetry class 222 (space group P2₁2₁2₁) to the monoclinic symmetry class 2 (space group P2₁). A distinct deflection pattern, resulting from the ferroelastic domain structure, occurs in the low temperature phase. The intensity of deflected beams varies considerably with temperature. Detailed studies revealed the structure of deflected spots during cooling–heating cycle. These spots change intensity, become more dispersed and finally split with decreasing temperature. Moreover, a variation of deflection angles was observed. A possible explanation of these phenomena is given in a framework of crystals optics.