Relaxation dynamics and fragility during liquid–glass transitions of poly(propylene glycol)s

The acoustic and thermal properties of the liquid–glass transitions of propylene glycol and its oligomers, poly (propylene glycol)s, were studied by temperature modulated DSC and Brillouin scattering. The fragility indices were determined from Angell plots using the observed modulation frequency dependence of the complex heat capacity. The variation in the glass transition temperatures is discussed on the basis of the free volume theory. The relaxation time of the structural relaxation obeys the Vogel–Fulcher law, and its high frequency end is in good agreement with the result of the dielectric measurement in the literature. The correlation between the observed thermal expansion coefficients and the glass transition temperature is discussed based on the free volume theory. The sound velocity and attenuation were accurately determined as a function of the temperature by Brillouin scattering by combination with the refractive index measurement. The relaxation dynamics were discussed by considering the relaxation from segmental motions. All of these physical properties were discussed based on the third-order anharmonicity and the Grüneisen parameter.     

弛豫法研究预交联颗粒凝胶的界面扩张流变性质

采用界面张力弛豫方法研究了一种新型聚合物--预交联颗粒凝胶(PPG)的界面流变性质, 考察了电解质及传统直链聚丙烯酰胺与PPG的相互作用对体系界面性质的影响, 计算得到了各体系界面扩张弹性和黏性的全频谱, 并通过归一法计算得到了相应的Cole-Cole图. 结果表明, 随着体相浓度的增加, PPG在界面层中形成网络结构, 界面扩张弹性和黏性大幅增强. 电解质能够中和PPG结构中的电荷, 明显降低扩张弹性和黏性. 直链聚丙烯酰胺与PPG在界面上可能形成更为复杂的结构, 膜的黏弹性由PPG决定.     

On the ionic conductivity of polymer electrolytes in terms of hole fraction

A theoretical model to interpret the conductivity of ions through polymer electrolytes is established in terms of the temperature and pressure‐dependent hole fraction computed from Simha‐Somcynsky hole theory. The model successfully linearizes the logarithm of PPG and PEG conductivity data with NaCF₃SO₃ in a 20:1 ratio for a broad range of temperature and pressure. The conductivity parameter and transmission coefficient with an additive hole fraction constant are discussed and compared for both species. The derivative of the logarithm of conductivity with respect to the hole fraction decreases inversely with the hole fraction and saturates at about 0.08 and 0.12 hole fractions for PPG and PEG, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2249–2254, 2008     

Sample cleanup-free determination of mycophenolic acid and its glucuronide in serum and plasma using the novel technology of ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry

Mycophenolic acid (MPA) is an immunosuppressant drug which powerfully inhibits lymphocyte proliferation. Since the early 1990s it has been used to prevent rejection in organ transplantation. The requirement of therapeutic drug monitoring shown in previous studies raises the necessity of acquiring accurate and sensitive methods to measure MPA and its major metabolite mycophenolic acid glucuronide (MPAG).The authors developed a sample cleanup-free, rapid, and highly specific method for simultaneous measurement of MPA and MPAG in human plasma and serum using the novel technology of ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry. MPA- and MPAG-determinations were performed during a 2.0-min run time. Multiple calibration curves for the analysis of MPA and MPAG exhibited consistent linearity and reproducibility in the range of 0.05-100 (r > 0.999) mg L⁻¹ and 4-4000 mg L⁻¹ (r > 0.999), respectively. Limits of Detection were 0.014 mg L⁻¹ for MPA and 1.85 mg L⁻¹ for MPAG. Lower Limits of Quantification were 0.05 mg L⁻¹ for MPA and 2.30 mg L⁻¹ for MPAG. Interassay imprecision was <10% for both substances. Mean recovery was 103.6% (range 78.1-129.7%) for MPA and 111.1% (range 73.0-139.6%) for MPAG. Agreement was good for MPA and MPAG between the presented method and a validated HPLC-MS/MS method. The Passing-Bablok regression line for MPA and MPAG was HPLC-MS/MS = 1.14 UPLC-MS/MS—0.14 [mg L⁻¹], r = 0.96, and HPLC-MS/MS = 0.77 UPLC-MS/MS + 0.50 [mg L⁻¹], r = 0.97, respectively. This sample cleanup-free and robust LC-MS/MS assay facilitates the rapid, accurate and simultaneous determination of MPA and MPAG in human body fluids.     

光电容积脉搏波的睡眠呼吸暂停综合征筛查方法

睡眠呼吸暂停综合征（SAS）素有“睡眠杀手”之称。由于其诊断金标准多导睡眠监测仪（PSG）的限制,诊断率一直偏低。由于呼吸暂停发生时会引发心率节奏的变化,因此利用心电图（ECG）通过心率变异性（HRV）分析可以实现SAS的自动筛查。但是,ECG-SAS方法所用电极穿戴繁琐、材质致敏性较高,影响睡眠安适度。鉴于脉率变异性（PRV）分析与HRV分析高度相关,并且光电容积脉搏波（PPG）信号相对ECG信号获取方式更加简单,不仅电极不易致敏,而且更易于穿戴,对睡眠干扰小。由此,提出利用同步采集的PPG信号和ECG信号,应用相同的建模方法,比较二者的疾病识别能力。应用反向传播（BP）神经网络,分别建立PPG-SAS与ECG-SAS自动筛查模型,并采用十折交叉验证法及受试者工作特征（ROC）曲线对模型进行对比与评估。实验数据来源于MIT-BIH Polysomnographic Database,共8 248个样本,其中正常样本6 227例。首先采用三层BP神经网络,默认参数下建立PPG-SAS与ECG-SAS模型,使用十折交叉验证法及ROC曲线进行模型分类准确性的对比;然后依次改变影响分类性能的隐层节点数、训练函数以及传递函数,建立多个PPG-SAS与ECG-SAS模型,从中选取各自的最优模型再进行对比。通过比较识别率、预测率以及ROC曲线面积,采用默认参数的PPG-SAS模型优于ECG-SAS模型。通过比较平均分类准确率,隐层节点数为50、训练函数为一步正割算法、隐含层传递函数为双曲正切S型函数时,PPG-SAS模型得到的最高识别率与预测率分别为80.30%和80.13%;隐层节点数为50、训练函数为一步正割算法、隐含层传递函数为径向基时,ECG-SAS模型的最高识别率与预测率分别为77.60%和77.67%。以上实验结果均表明PPG信号的SAS分类能力较ECG信号更具优越性,由此证明了PPG信号筛查SAS的可行性及可靠性,为临床SAS病症的早期发现及诊断率提升奠定理论基础。     

Determination of solubility parameters of cross-linked macromonomeric initiators based on polypropylene glycol

A new type macromonomeric azo initiators also named macroinimers, MIMs, based on polypropylene glycol, PPG, with molecular weight 400 and 2000, were synthesized. Self-condensing radical polymerization of the macroinimers gave cross-linked polypropylene glycols. The solubility parameters of the cross-linked polymers determined using swelling experiments in a series of solvents have been reported. Crosss-linked PPG-400 and cross-linked PPG-2000 indicated the same solubility parameter value. But their swelling ratios were different because of the differences of the chain lengths in between of the cross-points (Mc) of the gels. Therefore, while the largest swelling ratio exhibited by a cross-linked PPG-2000 in tetrahydrofurane was being 19.48, this ratio was 6.84 for the cross-linked PPG-400 in the same solvent. The solubility parameters and constant α for these cross-linked polymers were obtained as δ_{cross-linked PPG-400} = 9.56 (cal cm⁻³)^1/2, α = 0.123 cm³ cal⁻¹ and δ_{cross-linked PPG-2000} = 8.95 (cal cm⁻³)^1/2, α = 0.107 cm³ cal⁻¹ by using the least squares regression method.     

End-group characterisation of poly(propylene glycol)s by means of electrospray ionisation–tandem mass spectrometry (ESI-MS/MS)

The end-group functionalisation of a series of poly(propylene glycol)s has been characterised by means of electrospray ionisation–tandem mass spectrometry (ESI-MS/MS). A series of peaks with mass-to-charge ratios that are close to that of the precursor ion were used to generate information on the end-group functionalities of the poly(propylene glycol)s. Fragment ions resulting from losses of both of the end groups were noted from some of the samples. An example is presented of how software can be used to significantly reduce the length of time involved in data interpretation (which is typically the most time-consuming part of the analysis). Figure Screenshot from Polymerator software of annotated ESI-MS/MS spectrum from the lithiated heptamer of poly(propylene glycol) di-acrylate     

基于试验方差分析的血氧测量波长选取的研究

为了提高血氧饱和度光谱测量的精度和可靠性,增强血氧饱和度测量数据的有效性,提出了基于试验方差分析的血氧测量波长选取的方法。通过分析不同波长组合对应的血氧饱和度系数分布情况,合理地利用统计理论,从中选取较好的波长组合。实验中以不同血氧饱和度临床数据为基础,建立了不同波长组合(660和940 nm,660和805 nm,805和940 nm)计算出的血氧饱和度系数的单因素试验方差分析模型,参照分析模型中的F指标和p参数,比较分析不同波长组合的显著性,进而从光谱数据中选取出相对较好的波长组合,为进一步建模分析提供了可靠的中间数据。结果表明,选取660和805 nm的波长组合引入的总误差相对较小,能更显著的代表血氧饱和度的变化,相比其他的波长组合进行分析能够提高血氧测量精度。本研究将试验方差分析方法用于血氧测量中波长组合的优选,效果显著,为血氧饱和度的测量和其他相关光谱的特征波长选取以及定量分析提供了新思路。试验方差分析方法有助于从光谱中提取代表被测量的有效信息。     

一种光电容积脉搏信号的峰值点自动识别方法

光电容积脉搏信号的峰值点自动识别直接关系到无创血氧饱和度测量与脉搏波峰-峰间期提取的准确率。提出一种小波联合识别方法：基于小波多分辨率分析原理校正影响脉搏波峰值点幅值的基线干扰,再利用二次样条小波模极大算法自动识别峰值点。将该方法应用到自行研制的光电容积脉搏波测量系统中,对采集的信号进行了校正与峰值点识别,通过在信号中增加随机噪声以评价方法的稳定性与可靠性,然后利用10组实测数据,对比本方法与传统差分阈值法的峰值点识别准确率,进一步评价方法的有效性。结果表明：本方法在较好地消除了基线干扰的基础上,在染噪的信号中仍然会较精确地检测出脉搏波主波峰,具有较好的抗干扰能力,有利于提高血氧饱和度检测及峰-峰间期提取的准确性,从而有助于后期人体呼吸功能评价与心率变异性分析。     

基于PPG的心率和呼吸频率的测量研究

利用光电容积脉搏波描记法(PhotoPlethysmoGraphy,PPG)测量人体生理参数具有操作简单、性能稳定和适应性强等优点.采用反射式光电测量法获得桡动脉PPG信号,对PPG信号做快速傅里叶变换,分析频域实现人体心率和呼吸频率的检测.实验结果表明利用快速傅里叶变换获得的心率和呼吸频率与监护仪获得的相应数据之间有...