采用二维红外技术研究交联对碱溶胶原结构的影响

以N-羟基琥珀酰亚胺己二酸酯(NHS-AA)为交联剂,交联改性碱溶胶原,采用二维红外相关光谱法研究了交联对胶原二级结构的影响。研究发现,交联未影响胶原红外特征吸收峰的位置,但1672、1554和1241cm-1归属于胶原酰胺I带的CO伸缩振动、酰胺Ⅱ带的C—N伸缩与N—H弯曲振动和Ⅲ带的N—H面内变形振动峰之间存在同步正交叉峰,表明随交联共价键的增加,胶原的链段构象发生了变化。在NHS-AA用量增加的过程中,胶原二级结构变化的顺序为:酰胺Ⅲ带>酰胺Ⅰ带>酰胺Ⅱ带>—CH3>—CH—。由此可见,二维红外相关分析法能提供由交联引起的胶原构象动态变化的微观信息,为进一步研究改性胶原结构与功能之间的关系提供实验依据。     

胶原/透明质酸共混体系的相容性及相互作用研究

稀溶液粘度法研究表明,在纯水中,只有当透明质酸含量为10%时,共混物才相容;而氯化钠的加入,屏蔽了正电性的胶原分子与负电性的透明质酸分子之间的静电吸引力,从而避免了聚离子复合物形成,增强了胶原/透明质酸共混体系的相容性,使两者在任意比例都能相容。根据傅立叶红外光谱数据进行主成分分析研究表明,在纯水体系中,相容时胶原酰胺Ⅰ、Ⅱ、Ⅲ带与透明质酸的C—O—C、CO、N—H及C—OH之间形成氢键;而加入氯化钠后,只在胶原酰胺Ⅰ、Ⅱ带与透明质酸的CO、N—H及C—OH之间形成氢键。     

红外光谱法氧化石墨烯羧基官能团含量的测定

建立一种红外光谱法测定氧化石墨烯中羧基对应氧化度的方法。利用改进Hummers法制备氧化石墨烯(GO),基于苯甲酸具有类似结构的原理,采用苯甲酸作为标准物质,苯甲酸傅里叶红外光谱在1 591,1504,1 423 cm-13处为苯环骨架伸缩振动特征吸收峰,在1 692 cm-1处为羧基中C=O的伸缩振动特征吸收峰,而GO的傅里叶红外光谱在1 630 cm-1为类苯环架构C=C的伸缩振动,在1 730 cm-1为羧基中C=O的伸缩振动特征吸收峰,这样,可利用苯甲酸上苯环和羧基中C=O的峰面积比值与GO上C=C和羧基中C=O的峰面积比值,通过结构分析和相关公式的计算,得到氧化度的值。并且利用紫外可见光谱,X衍射光谱,拉曼光谱,以及原子力显微镜对其进行对比验证,证明红外光谱的方法可行。可为氧化石墨烯羧基氧化度的测定提供一种操作简单、行之有效的方法。     

微波ECR-CVD法制备a-C:F:H膜的红外吸收及其光学带隙

改变CHF3 CH4 流量比R =[CHF3] ([CHF3]+[CH4 ]) ,采用微波电子回旋共振等离子体化学气相沉积 (MWECR CVD)方法沉积a C :F :H薄膜。a C :F :H薄膜的结构和光学带隙使用傅立叶变换红外光谱和紫外 可见光谱来表征。红外结果表明 ,在低流量比R(R <6 4 % )下 ,薄膜的红外特征结构主要以 CF(10 6 0cm- 1 ) , CF2(112 0cm- 1 )以及 CHx(2 80 0～ 30 0 0cm- 1 )的伸缩振动为主 ;在高流量比R(R >6 4 % )下 ,薄膜表现为类聚四氟乙烯(PTFE)的结构特征 ,典型的红外特征峰是位于 12 2 0cm- 1 处的 -CF2 反对称伸缩振动。薄膜的光学带隙Eg 随流量比R的变化表现为先降后升。进一步研究表明 ,薄膜中的H和F浓度调制着薄膜的CC共轭双键结构 ,使光学带隙Eg 从 2 37到 3 3之间变化     

聚四氟乙烯F-C-F伸缩振动二维红外光谱研究

在303~393K的温度范围内,测定聚四氟乙烯F-C-F伸缩振动模式(νCF2)的一维红外光谱。研究发现:1220cm-1的红外吸收峰归属于聚四氟乙烯F-C-F不对称伸缩振动模式(νasCF2),而1150cm-1的红外吸收峰则归属于聚四氟乙烯F-C-F对称伸缩振动模式(νsCF2)。进一步研究了聚四氟乙烯νCF2的二阶导数红外光谱、四阶导数红外光谱,发现聚四氟乙烯νasCF2在1210cm-1和1260cm-1处裂分为双峰;而聚四氟乙烯νsCF2则在1145cm-1、1155cm-1和1175cm-1裂分为3个吸收峰。最后研究了聚四氟乙烯二维红外光谱,考察了温度对于聚四氟乙烯νCF2吸收强度变化的影响。研究发现:随着测定温度的升高,聚四氟乙烯νCF2红外吸收强度变化快慢的顺序为:1145cm-1>1210cm-1>1155cm-1>1175cm-1>1260cm-1。本项研究拓展了二维红外光谱在聚四氟乙烯热变性方面的研究范围。     

聚四氟乙烯F-C-F伸缩振动二维红外光谱研究

在303~393K的温度范围内,测定聚四氟乙烯F-C-F伸缩振动模式(νCF2)的一维红外光谱。研究发现:1220cm-1的红外吸收峰归属于聚四氟乙烯F-C-F不对称伸缩振动模式(νasCF2),而1150cm-1的红外吸收峰则归属于聚四氟乙烯F-C-F对称伸缩振动模式(νsCF2)。进一步研究了聚四氟乙烯νCF2的二阶导数红外光谱、四阶导数红外光谱,发现聚四氟乙烯νasCF2在1210cm-1和1260cm-1处裂分为双峰;而聚四氟乙烯νsCF2则在1145cm-1、1155cm-1和1175cm-1裂分为3个吸收峰。最后研究了聚四氟乙烯二维红外光谱,考察了温度对于聚四氟乙烯νCF2吸收强度变化的影响。研究发现:随着测定温度的升高,聚四氟乙烯νCF2红外吸收强度变化快慢的顺序为:1145cm-1>1210cm-1>1155cm-1>1175cm-1>1260cm-1。本项研究拓展了二维红外光谱在聚四氟乙烯热变性方面的研究范围。     

纤维素-钙纤维的制备及阻燃性能表征

将纤维素纤维接枝马来酸酐后,与Ca CO3反应得的到含钙离子的纤维素-钙纤维,利用傅里叶变换红外光谱、极限氧指数、锥形量热对其燃烧性能及热稳定性进行了表征。傅里叶红外光谱在2597 cm-1的羧基O-H伸缩振动和1214cm-1的CO-OH的伸缩振动及纤维样品在在2500~2800 cm-1区间内吸收峰的变化证明了接枝方法的可行性和纤维素-钙纤维成功制备。极限氧指数测试结果发现含有钙离子的纤维素纤维的阻燃性明显提高。通过锥形量热测试表明,钙离子促使纤维素纤维生成更多的残炭,降低了纤维燃烧过程中的热释放量。扫描电子显微镜对热解残渣分析表明,钙离子在纤维素纤维中的含量越高,残渣表面越致密,纤维阻燃性越好。最后提出钙离子对纤维素纤维的阻燃机理。     

等离子体气相沉积非晶SiO2薄膜的特性研究

用傅立叶红外吸收光谱 ,电子自旋共振 ,表面台阶仪等研究了等离子体增强化学气相沉积法制备的非晶SiO2 薄膜的特性与膜厚的关系。当膜厚从 0 1 μm递增到 1 1 μm时 ,1 0 60cm- 1 附近的Si—O—Si伸缩振动吸收峰从 1 0 50cm- 1 漂移到1 0 75cm- 1 ,但是 80 0cm- 1 处的Si—O—Si弯曲振动吸收峰不随膜厚变化而变化。通过比较 ,由于多重反射而引起的Si—O—Si伸缩振动吸收峰漂移的理论计算值 ,认为本研究中的Si—O—Si伸缩振动吸收峰的漂移不仅是由于多重反射效应 ,而且更主要是由于薄膜的物理性能随膜厚增加而发生了变化。Si悬挂键密度、应力以及HF缓冲溶液中的腐蚀速度等实验结果验证了以上的观点     

PVA/HPC相容性及共混膜的性能

共混改性是提高材料性能的简便而有效的方式,文中以聚乙烯醇(PVA)和羟丙基纤维素(HPC)为基本成膜材料,通过制备不同配比的共混溶液,探讨了PVA/HPC共混体系的相容性,并对共混膜的结构和性能进行了初步表征。稀溶液黏度法和扫描电镜分析表明,共混体系中PVA含量较多(80%)时,共混膜呈现均一的相态结构,共混体系为相容体系;傅立叶红外光谱和热重分析显示,PVA/HPC共混体系中存在的氢键作用提高了共混体系的热稳定性。     

聚乳酸/柠檬酸三丁酯固-液共混材料的制备与性能研究

采用双螺杆挤出机液体进料工艺,制备了聚乳酸/柠檬酸三丁酯(PLA/TBC)固-液共混材料,表征了其性能。结果表明:双螺杆挤出机液体进料工艺能够精确控制TBC在PLA中的质量分数;傅里叶红外光谱仪微观结构表征了2877cm-1特征峰的出现、羟基伸缩振动峰红移,证明TBC对PLA起到了增塑作用;当TBC含量为16%(质量分数)时共混材料从脆性材料转变为韧性材料;降解实验显示,这种共混薄膜在6个月内性能基本消失,轻微受力时薄膜粉碎。     

PECVD非晶SiOx∶H薄膜的Si—O—Si键红外吸收特性研究

用傅里叶红外光谱(FT-IR)测试分析了等离子体化学气相沉积法沉积的非晶SiOx∶H(0≤x≤2.0)薄膜中的Si—O—Si伸缩振动模与氧含量x的关系。Si—O—Si伸缩振动模在1000和1150cm     

Perturbation-correlation moving-window two-dimensional correlation spectroscopy

A new method of analysis, perturbation-correlation moving-window two-dimensional (PCMW2D) correlation spectroscopy, is proposed. For a spectral data set collected under an external perturbation, this method provides a pair of synchronous and asynchronous two-dimensional correlation spectra plotted on a plane between a spectral variable (e.g., wavenumber) axis and a perturbation variable (e.g., temperature) axis. One of the advantages of this new correlation analysis method is that complicated spectral variation along the perturbation direction can be monitored. It has been found that the synchronous and asynchronous PCMW2D correlation spectra are similar to the first perturbation derivative and negative second perturbation derivative spectra of the original data, respectively. To demonstrate the potential of PCMW2D correlation spectroscopy, it has been applied to temperature-dependent infrared (IR) spectra of a poly(vinyl alcohol) (PVA) film. The thermal behavior of the PVA film has been revealed by the PCMW2D correlation analysis. Two characteristic cross-peaks are observed in the synchronous PCMW2D correlation spectra generated from the temperature-dependent IR spectra between the crystalline phase C-O stretching band at 1141 cm-1 and the melting temperature of 209 degrees C and between the amorphous phase C-O stretching band at 1095 cm-1 and another specific temperature of 233 degrees C. This specific temperature of 233 degrees C corresponds to the thermal degradation temperature due to the elimination of the hydroxyl group attached to the main chain.     

Insight into the molecular arrangement of high-density polyethylene polymer chains in blends of polystyrene/highdensity polyethylene from differential scanning calorimetry and Raman techniques

Polystyrene/high-density polyethylene (PS/HDPE) blends were synthesized by melt blending in a single screw extruder. Co-continuity measurements using solvent extraction and scanning electron (SEM) micrographs showed that co-continuity was obtained around 35% PS. Thermal analyses measurements revealed a reduction in crystallinity of the HDPE phase around the co-continuous composition. Raman analyses across the entire composition range of these blends showed an increase in the normalized integral intensities of the 1128 cm(-1) and 1061 cm(-1) stretching vibrations of the HDPE molecules. The presence of all-trans HDPE chains that are not packed into an orthorhombic structure is used to explain the simultaneous occurrence of reduced crystallinity and increased intensity of all-trans HDPE stretch vibrations.     

Use of infrared spectroscopy for the determination of electronegativity of rare earth elements

Infrared spectroscopy has been used to study a series of synthetic agardite minerals. Four OH stretching bands are observed at around 3568, 3482, 3362, and 3296 cm(-1). The first band is assigned to zeolitic, non-hydrogen-bonded water. The band at 3296 cm(-1) is assigned to strongly hydrogen-bonded water with an H bond distance of 2.72 A. The water in agardites is better described as structured water and not as zeolitic water. Two bands at around 999 and 975 cm(-1) are assigned to OH deformation modes. Two sets of AsO symmetric stretching vibrations were found and assigned to the vibrational modes of AsO(4) and HAsO(4) units. Linear relationships between positions of infrared bands associated with bonding to the OH units and the electronegativity of the rare earth elements were derived, with correlation coefficients >0.92. These linear functions were then used to calculate the electronegativity of Eu, for which a value of 1.1808 on the Pauling scale was found.     

Two-dimensional correlation study of uniaxially drawn poly(ethylene terephthalate) films by using attenuated total reflection based dynamic compression modulation step-scan fourier transform infrared in combination with spectral simulation analysis by density functional theory

Attenuated total reflection (ATR) based dynamic compression modulation two-dimensional (2D) correlation studies of uniaxially drawn poly(ethylene terephthalate) (PET) films have been performed in combination with spectral simulation analysis by density functional theory (DFT). The dynamic 2D infrared (IR) correlation spectra in the region of the CCO stretching mode vibrations show four distinct correlation peaks located around 1290, 1265, 1248, and 1234 cm(-1). These bands can be clearly assigned to the combination bands or coupling modes of the CH in-plane bend of the benzene ring or the CH(2) deformation of the ethylene glycol unit, as well as CCO stretching vibrations, which are gauche conformer's characteristic bands, by DFT analysis. The sequential analysis of 2D correlation data shows that, upon applying the dynamic compression, the response of the side chain regions (ester groups) occurs first, followed by that of the backbone regions (benzene rings). The ATR based dynamic compression modulation 2D correlation spectroscopy in combination with DFT analysis can be a powerful tool for various polymer characterizations.     

Tailoring the Release Rates of Fluconazole Using Solid Dispersions in Polymer Blends

Formulations of the drug Fluconazole with different release characteristics were prepared by dispersing the active pharmaceutical ingredient (API) in various polymeric carriers, and especially in polymer blends. Fluconazole was tested as a model drug with low solubility in water. First solid dispersions in pure polymers were studied. Use of pure polyvinylpyrrolidone (PVP) as carrier even for high drug load (30 wt%) resulted in rapid release. The drug release rates decreased by increasing the API content. The dissolution rate enhancement was attributed to drug amorphization, particle size reduction, and possible improvement of the drug wetting characteristics. Hydroxypropyl methylcellulose (HPMC) gave solid dispersions, from which the release rates of the drug varied from immediate to sustaining. As the drug amount increased, the rates became higher. Similar behavior also was found when Chitosan was used as carrier, with much more controlled rates close to those for sustained release. These differences were mainly attributed to the limited solubility and swelling of HPMC and Chitosan in aquatic media. To study the effectiveness of polymer blends in adjusting the release rates of the drug, solid dispersions in PVP/HPMC and PVP/Chitosan miscible blends were studied. The release rates of Fluconazole were adequately adjusted by differentiating the weight ratio of the polymers in the blends. PVP/HPMC blends with high PVP content can be used for immediate release formulations but PVP/Chitosan blends are inappropriate for such formulations and can only be used for controlled release.     

Tailoring the release rates of fluconazole using solid dispersions in polymer blends

Formulations of the drug Fluconazole with different release characteristics were prepared by dispersing the active pharmaceutical ingredient (API) in various polymeric carriers, and especially in polymer blends. Fluconazole was tested as a model drug with low solubility in water. First solid dispersions in pure polymers were studied. Use of pure polyvinylpyrrolidone (PVP) as carrier even for high drug load (30 wt%) resulted in rapid release. The drug release rates decreased by increasing the API content. The dissolution rate enhancement was attributed to drug amorphization, particle size reduction, and possible improvement of the drug wetting characteristics. Hydroxypropyl methylcellulose (HPMC) gave solid dispersions, from which the release rates of the drug varied from immediate to sustaining. As the drug amount increased, the rates became higher. Similar behavior also was found when Chitosan was used as carrier, with much more controlled rates close to those for sustained release. These differences were mainly attributed to the limited solubility and swelling of HPMC and Chitosan in aquatic media. To study the effectiveness of polymer blends in adjusting the release rates of the drug, solid dispersions in PVP/HPMC and PVP/Chitosan miscible blends were studied. The release rates of Fluconazole were adequately adjusted by differentiating the weight ratio of the polymers in the blends. PVP/HPMC blends with high PVP content can be used for immediate release formulations but PVP/Chitosan blends are inappropriate for such formulations and can only be used for controlled release.     

Nature of hydrogen bonding of water molecules in aqueous solutions of glycerol by attenuated total reflection (ATR) infrared spectroscopy

Attenuated total reflection infrared (ATR-IR) spectroscopy was performed on glycerol/water solutions in order to gain a better understanding of the strong hydrogen bonding of glycerol as a humectant. The OH stretching band after eliminating the contribution of glycerol OH in the glycerol/water solutions was decomposed using three Gaussian components. With increasing glycerol concentrations up to 50 volume %, the decrease of the 3428 cm(-1) component (middle H-bond component) and the increase of the 3562 cm(-1) component (longer H-bond component) suggested the breaking of H bonds among water molecules. On the other hand, the 3242 cm(-1) component (shorter H-bond component) remained unchanged. It was expected that water molecules surrounding glycerol molecules are retained by strong H bonding between H atoms of water and O atoms in C-O of glycerol when aqueous solutions containing glycerol are introduced in human skin.     

基于HTEMPO聚己内酯-聚苯乙烯嵌段共聚物的合成

以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(HTEMPO)为引发剂,采用配位-插入开环聚合(CROP)的方法引发ε-己内酯聚合,然后利用氮氧稳定自由基聚合(NMRP)调控苯乙烯聚合得到聚己内酯-聚苯乙烯嵌段共聚物(PCL-b-PS),并对此过程进行了动力学研究,结果表明,聚苯乙烯链段的分子量可控,符合活性聚合特征。通过GPC测定,共聚物的分子量分布范围是1.26~1.37。在FT-IR图上可以看到属于PCL-b-PS的特征峰,分别为3470 cm-1、1726 cm-1、1192cm-1、1047 cm-1、1600 cm-1、1493 cm-1和1453 cm-1处的羟基、羰基C-O-C的对称和不对称伸缩振动、苯环的骨架振动吸收峰。在1H-NMR谱图上,有δ=1.3~1.68、4.08的己内酯亚甲基氢的化学位移和6.30~7.20苯环上氢的化学位移。