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.     

碘稳频中红外差频激光光谱技术

为实现中红外波段的高精度线型研究,建立了一套在2.5～5um波段连续可调谐的中红外差频激光光谱测量系统.基于宽带连续可调谐钛宝石激光器(700 ～900 nm)和单频连续Nd:YAG激光器(1064 nm),利用碘多普勒展宽吸收和频率调制技术,对Nd:YAG激光的频率进行反馈控制,使1064 nm的Nd:YAG激光的波长稳定性好于1X10-5 cm-1由此差频输出的波长稳定性达到1×10-1cm-1水平,适合高精度的线形研究.并通过对CH4分子在2927 cm-1附近吸收谱线的测量,表明该系统可以结合频率调制方法,进行高灵敏的光谱检测.     

The Effect of Hydrophilic Bentonite Nanoclay on the Thermogelation Properties of Poly(N-isopropylacrylamide)-poly(ethylene glycol)-poly(N-isopropylacrylamide) Triblock Copolymer Aqueous Solutions

The effect of hydrophilic bentonite addition on the thermogelation properties of aqueous solutions of poly(N-isopropylacrylamide)–poly(ethylene glycol)–poly(N-isopropylacrylamide) (PNIPAM-PEG-PNIPAM) triblock copolymers of various compositions and molecular weights was investigated. Dynamic rheometry and differential scanning calorimetry (DSC) measurements showed that increasing concentrations of clay added to 20 wt.% polymer aqueous solutions caused a decrease of the temperature at which the viscosity starts increasing, while the temperature corresponding to the maximum endothermic effect due to the PNIPAM chain dehydration remained practically unchanged. The storage modulus, G′, increased with clay concentration for shorter PNIPAM chain triblock copolymers, while an opposite situation occurred in the case of the block copolymer with the longest PNIPAM block. For bentonite concentrations above 1 wt.%, G′ was larger than the viscous modulus, G″, at temperatures higher than the phase separation temperature, indicating a predominantly elastic character of the resulting composite hydrogels. These findings were explained through the presence of polymer–clay interactions occurring mainly through the PEG blocks.     

Luminescent Behavior of two Novel Thermo-Sensitive Poly(N-isopropylacrylamide) Hydrogels Incorporated with Rare Earth Complexes

Two novel luminescent temperature-sensitive poly(N-isopropylacrylamide) hydrogels fabricated with rare earth (Eu, Tb) picolinic acid complexes were in-situ synthesized within the interpenetration networks. Fluorescence spectra indicate the two functional gels exhibit red for Eu³⁺ species and green emissions for Tb³⁺ ones, respectively, whose luminescence intensities are changed due to temperature increasing from 5 to 30°C until totally quenched at lower critical solution temperature (33°C). In addition, the decreasing luminescence behavior obeys the simple linear equations. The releasing experiment substantiates that there may be complexation between O⩵C–NH⩵ moieties of P-NIPAA and Eu³⁺ ions for the prolonged released time.     

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.     

The phase transition of poly(N-isopropylacrylamide): the effect of aging

We study the effect of temporal and thermal aging of linear and hydrogel samples of poly(N-isopropylacrylamide) (PNIPAM). For this purpose, we designed a simple and inexpensive experimental device able to measure the optical density as a function of temperature. The samples were aged from 4 to 14 days at two temperatures: 24 and 37°C. We found that the phase transitions of linear PNIPAM samples shift to lower or higher temperatures, depending on the storage conditions, while the phase transitions of hydrogels always shift to higher temperatures. Structural differences between linear and hydrogel PNIPAMs and the formation of additional hydrogen bonds are behind these shifts.     

Synthesis and spectral-luminescent properties of poly(N-isopropylacrylamide)

The spectral-luminescent characteristics of water and methanol solutions of polymers containing tetraphenylporphyrin substituents were investigated. The water-soluble polymer was obtained by the interaction of poly(N-isopropylamide) containing N-oxysuccinimide substituents with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin. From the synthesized polymer its analog with Zn-porphyrin substituents was obtained. This phenomenon is attributed to the specific features of the conformational behavior of polymeric chains in water solutions. Water solutions of polymers experience a thermally reversible phase transition upon heating, which is accompanied by a considerable enhancement of light scattering. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 483–487, July–August, 2000.     

Preparation and Property of Poly(N-isopropylacrylamide) (PNIPAAm)/Clay/Linear Polyacrylamide (PAAm) Nanocomposite Hydrogels

In this study, a linear polyacrylamide (PAAm) with an average viscosimetric molecular weight 3.97 × 10³ kg mol^?1 was added to the prereaction solution for the preparation of poly(N-isopropylacrylamide) (PNIPAAm)/clay nanocomposite hydrogels. The effects of the linear PAAm on the optical transparency and tensile property of the resulting PNIPAAm/clay/linear PAAm hydrogels were systematically investigated. The results revealed that the optical transparency and mechanical tensile properties of the resultant hydrogels strongly depended on the linear PAAm content. In particular, 5 wt% loading of linear PAAm led to almost fivefold decreases of transmittance at 25°C and a onefold increase of the tensile elongation at break. These characteristic changes were explained by a typical interpenetrating microstructure, which was formed by PNIPAAm due to the incorporation of linear PAAm in the PNIPAAm/clay network. The dynamic rheological test and infrared spectroscopy analysis on the mixed solutions consisting of linear PAAm and clay platelets further confirmed the interaction.     

基于LIBS技术的钢铁合金中Cr和Ni元素SVM定量分析方法研究

针对钢铁合金样品中存在基体效应复杂的问题,通过优化支持向量机模型的输入特征,建立多元素变量的定量分析模型,预测钢铁合金样品中Cr和Ni元素的含量。研究结果表明,分别以特征谱线的峰值强度和积分强度作为支持向量机模型的输入时,积分强度因为包含了谱线的谱宽和形状信息,模型训练效果较好;相比于单一元素谱线的特征信息,采用多元素的多条谱线信息输入支持向量机模型时,模型训练效果较好,这是由于多种谱线信息的输入可以有效校正基体效应的影响。在此基础上,通过归一化变量将内标法与多变量定标方法有效结合,不仅可以减小实验测量误差还能有效校正基体效应的影响,而且有效提高了模型的重复率和准确率。归一化变量作为支持向量机模型的输入变量,对待测样品S₁和S₂中Cr元素含量预测的相对误差为6.58%和1.12%,对Ni元素浓度预测的相对误差为13.4%和4.71%。通过归一化变量将内标法与多变量定标方法有效结合,可以充分发挥SVM算法的非线性学习优势,为LIBS技术应用于复杂样品定量定标分析提供理论基础。     

激光诱导击穿光谱用于NaCl溶液中Na元素含量分析

为了研究Na元素在水中的检测灵敏度,采用激光诱导击穿光谱检测NaCl溶液中的Na元素。选择NaⅠ589.0 nm和NaⅠ589.6 nm作为分析谱线,利用配置的六种浓度的NaCl溶液,采用外标法、内标法以及小波变换降噪法,给出了NaCl溶液中Na元素的定标曲线。发现通过内标法获得的定标曲线的线性相关系数r达到0.998,优于外标法（r=0.985）,并且优于小波降噪后外标法（r=0.986）。相对外标法而言,小波变换降噪法有效降低了LIBS光谱中的连续背景光谱噪声,使LIBS的RSD从5.68%降至1.61%,从而使LOD值从50.8 μg·mL-1降至19.54 μg·mL-1, 内标法选择NaⅠ589.0 nm和NaⅠ589.6 nm钠原子谱线与内标参考谱线HⅠ656.2 nm氢原子谱线强度比值能有效的克服实验条件波动带来的影响,因此,内标法给出的NaCl溶液中Na元素的定标曲线的线性相关系数最大。而对于小波变换降噪处理方法,能够有效的降低LIBS光谱的连续背景带来的噪声,但不能克服实验条件波动对LIBS光谱信息的影响,因此小波变化降噪方法能够提高LIBS的RSD,但对降噪处理后的外标法给出的定标曲线的线性相关系数的提高影响不大。说明内标法有效的提高了检测灵敏度,减弱了实验条件波动带来的影响,定标曲线具有更好的线性相关性。而小波变换降噪处理后有效降低了LIBS光谱中的连续背景光谱噪声,实现LIBS检测限变低。谱线NaⅠ589.0 nm为分析谱线得到的RSD和LOD值小于以谱线NaⅠ589.6 nm为分析谱线的结果,NaⅠ589.0 nm和NaⅠ589.6 nm这两谱线的上能级分别为2.104和2.102 eV, 发现分析谱线的上能级对NaCl溶液中的Na元素的RSD和LOD值有影响,存在上能级大,而RSD和LOD值较小的现象。研究结果表明,LIBS技术可以实现溶液中元素的原位实时检测,并在水污染检测方面受到广泛关注。     

Tuning of Lower Critical Solution Temperature (LCST) of Poly(N-Isopropylacrylamide-co-Acrylic acid) Hydrogels

Temperature-responsive hydrogel with a lower critical solution temperature (LCST) close to human body temperature was prepared. Crosslinked N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) copolymer networks were synthesized at various monomer ratios in the presence of ammonium persulfate (APS), N,N′-methylenebisacrylamide (NMBA) and N,N,N′,N′-tetramethylethylenediamine (TEMED) via a redox polymerization method. The resulting hydrogels possessed thermo- and pH-responsive characteristics. They were characterized in terms of swelling ratio, volume change, water uptake and diffusivity, water vapor uptake and diffusivity, and phase transition temperature. The water liquid and vapor diffusion coefficients for all the synthesized hydrogels were higher than the literature data, implying higher rates for drug release. The LCST of the hydrogel increased with higher AAc content in the copolymer. The gel containing 1.8% AAc exhibited an LCST similar to human body temperature, demonstrating a potential use in drug controlled release and biomedical applications.     

Determination of the debris produced from poly(ethylene terephthalate) during KrF excimer laser ablation

Pulsed UV laser beams, which are widely used in the processing of polymers, have many advantages because their photon energy is higher than the binding energy of polymers. Fabricating polymers with a UV laser process is faster, cleaner, and more convenient than with other processes. Nevertheless, some problems occur in the precision microprocessing of polymers. For example, the formation and deposition of surface debris, which is produced from the breakdown of either polymer chains or radical bonds.To determine the formation and origin of surface debris, a KrF excimer laser beam (248 nm) was used in the processing of poly(ethylene terephthalate) (PET). The investigation of the debris formation was facilitated by UV-vis spectroscopy, ATR FT-IR spectroscopy, and NMR spectroscopy. The UV-vis absorption peak indicates that the primary chromophore in the PET is benzoate. Furthermore, because benzoate causes the primary absorption, the absorbed energy is transferred by heat generation to an unsaturated ester. The ATR FT-IR spectrometer measurements show that the phenyl systems in the benzoate are demolished by ablation. This phenomenon indicates that the photochemical reaction causes the benzoate bonds to break down, and this breakdown in turn causes the carbonization to leave debris on the PET.