用傅里叶变换红外光谱法研究聚对苯二甲酸乙二酯的结构

用傅里叶变换红外光谱法,将一系列不同温度下退火的PET光谱与熔融淬火的PET光谱进行数字吸光度相减,得到不同结晶状态的“反式构象光谱”。进一步将不同温度退火的“反式构象光谱”(240℃和120℃)彼此相减,可得到“纯晶区的光谱”和“非晶区的反式构象光谱”。通过差示光谱的比较,发现一些新的谱带和谱带的变化。可用PET 的晶区和非晶区中其分子链的内旋转构象的变化解释。     

聚对苯二甲酸乙二酯非晶区反式构象结构的探讨

<正> 聚对苯二甲酸乙二酯(PET)的重复单元中有乙撑基。它的碳碳键内旋转产生反式构象(T)和左右式构象(G)。用其不同的构象来表征PET的聚集态结构,对研究结构与性能的关系是十分重要的。许多工作都已指出,乙撑基反式构象的谱带热处理时随结晶度的增加而增加。X-射线衍射的结果证实     

变温红外法研究聚对苯二甲酸乙二酯分子链的松弛运动及其构象转变

在30～170 ℃范围内逐渐升温过程中,用红外光谱仪原位检测无定形聚对苯二甲酸乙二酯（PET）薄膜红外光谱图的变化情况。通过特征谱带吸光度与温度的变化特点,研究了PET分子链在热变化过程中的松弛运动及冷结晶过程中分子链的构象变化。实验结果表明在冷结晶过程中,随PET结晶的不断完善,对应左右式(gauche)构象的吸收峰减弱,对应反式(trans)构象的吸收峰增强,并计算出CH2面外摇摆振动结晶前和结晶后反式构象和左右式构象的相对百分含量随温度的变化关系,以及玻璃化转变和冷结晶的温区范围。     

硬弹性聚丙烯晶相和非晶相分子链取向的研究

本文用力学-振动光谱研究了硬弹性聚丙烯(HEPP)晶区和非晶区分子链在拉伸时取向的变化.我们发现在红外光谱中,1130—1190cm~(-1)波数范围内存在着三个峰,其中1167cm~(-1)处的峰是与结晶相长螺旋分子链相关的构象谱带,其谱带的强弱变化是与998cm~(-1)结晶谱带在拉伸时的变化趋势一致的.1159cm~(-1)谱带能够被归属于无定形谱带.而1152cm~(-1)处的峰也许是与短螺旋分子链构象谱带相关的.我们用计算机的二次微分、解卷积以及分峰程序测定了拉伸时HEPP晶区和非晶区分子链的取向函数,结果发现HEPP无定形分子链取向随拉伸比增加而增加,而晶区分子链的取向随拉伸比的增加先下降,直至拉伸比为1.5(第二次屈服点)后才逐渐增加.     

变温傅里叶红外光谱技术研究硬脂酸C-H伸缩振动

采用傅里叶红外光谱技术研究了温度对于硬脂酸C-H伸缩振动、分子脂肪链构象改变和分子间作用力的影响。运用变温红外技术在293~393K范围内,分别测定了硬脂酸C-H的一维红外光谱、二阶导数红外光谱、四阶导数红外光谱和去卷积红外光谱。结果表明:1在293~333K范围内,一维红外光谱中2 965,2 870cm-1附近的弱吸收谱带分别归属于甲基的不对称伸缩振动模式νas(-CH3)和对称伸缩振动模式νs(-CH3),相应的导数光谱及去卷积红外光谱能提高一维红外谱的分辨率;2在293~333K范围内,硬脂酸脂肪链处于全反式构象,在348~353K范围内,硬脂酸分子脂肪链构象由全反式构象向无序构象转变;3随着测量温度的升高,硬脂酸分子间的作用力不断降低。     

CuCl_2对聚乙二醇(PEG)构象和结晶行为的影响

用傅里叶变换红外光谱法(FT-IR)、差示扫描量热法(DSC)、广角X射线衍射法(WAXD)研究了少量过渡金属盐氯化铜(CuCl_2)对聚乙二醇(PEG)构象和结晶行为的影响.Cu~(2+)与PEG分子链中的氧原子有配位键生成,通过溶液电导率的测定,发现一个Cu~(2+)大约与3个PEG链节单元形成配位结构,从而使PEG的构象和结晶行为发生变化,随着体系中CuCl_2含量的增加,PEG分子链中OC-CO旁式构象相对反式构象含量逐渐增加,在CuCl_2含量(w)为7%左右时达到极大值,在CuCl_2含量(w)为9%时,反而是反式构象相对旁式构象含量多些.混合物中PEG的结晶度随着体系中CuCl_2含量的增加逐渐降低,含量(w)为9%时,又有所提高.     

CuCl2对聚乙二醇（PEG）的构象和结晶的影响

用傅里叶变换红外光谱法(FT-IR)、差示扫描量热法(DSC)、广角 X射线衍射法(WAXD)研究了少量过渡金属盐氯化铜(CuCl2)对聚乙二醇(PEG)构象和结晶行为的影响. Cu2＋与PEG分子链中的氧原子有配位键生成, 通过溶液电导率的测定, 发现一个Cu2＋大约与3个PEG链节单元形成配位结构, 从而使PEG的构象和结晶行为发生变化, 随着体系中CuCl2含量的增加, PEG分子链中OC—CO旁式构象相对反式构象含量逐渐增加, 在CuCl2含量(w)为7%左右时达到极大值, 在CuCl2含量(w)为9%时, 反而是反式构象相对旁式构象含量多些. 混合物中PEG的结晶度随着体系中CuCl2含量的增加逐渐降低, 含量(w)为9%时, 又有所提高.     

超高分子量聚乙烯的红外光谱的特性研究

研究了超高分子量聚乙烯(M_w>1×10⁵)的红外光谱-温度特性.3条非晶谱带(1368、1352和1304cm^-1)的吸收强度均随温度升高而增大,但都比普通分子量聚乙烯增加的小,尤以高于140℃更甚.分子链中次甲基的近程构象序列分布随温度的变化不受分子量的影响,但旁式构象序列分布则随温度升高而增大.升温和降温过程的红外光谱均表明1352和1304cm^-1两谱带随结晶状态的变化比1368cm^-1更敏感.     

青蒿素的Raman光谱研究

本文对固态青蒿素的FT-Raman光谱和普通Raman光谱以及低浓度(1×10^-^5mol/L)青蒿素水溶液的表面增强Raman散射(SERS)光谱进行了检测, 着重观察了1756cm^-^1六元内酯环振动谱带, 发现其在FT-Raman和普通Raman光谱中表现为强振动, 而在SERS光谱中此振动谱带消失, 说明分子内酯环发生了破裂。根据1756cm^-^1谱带的变化以及724cm^-^1过氧基团振动频率的位移, 对青蒿素在银表面上的吸附取向进行了研究。还研究了青蒿素与氯高铁血红素的作用情况, 发现两者作用后, 明显改变了青蒿素在银表面上的吸附。     

嵌段共聚物傅里叶变换拉曼光谱

用傅里叶变换拉曼光谱(FT-Paman)研究了聚环氧乙烷-聚环氧丙烷-聚环氧乙烷(PEO-PPO-PEO)嵌段共聚物的无水样品,发现某些谱带对PEO0-PPO-PEO嵌段共聚物的结构和构象变化敏感,其中某些峰的相对强度的PPO/PEO比率和共聚物的构象有关,研究表明PluronicF68和F88具有一些反式构象的螺旋结构,PluronicP103(P123)是无规则结构,其它的嵌段共聚物处于二者之间.     

Structural and conformational changes during thermally‐induced crystallization of poly(trimethylene terephthalate) by infrared spectroscopy

Conformational changes occurring during thermally‐induced crystallization of poly(trimethylene terephthalate) (PTT) by annealing have been studied using density measurement, differential scanning calorimetry (DSC), and mid‐infrared spectroscopy (MIR). Infrared spectra of amorphous and semicrystalline PTT were obtained, and digital subtraction of the amorphous contribution from the semicrystalline PTT spectra provided characteristic MIR spectra of amorphous and crystalline PTT. The normalized absorbance of 1577, 1173, and 976 cm^?1 were plotted against the crystallinity showing that these bands can be used unambiguously to represent the trans conformation while the band at 1358 cm^?1 can be used to represent gauche conformation of methylene segment. The presence of a weak band at 1358 cm^?1 in the amorphous spectrum suggested that a small amount of gauche conformation is present in the amorphous phase. Infrared spectroscopy has been used for the first time as a means to estimate the trans and gauche conformations of methylene segments in PTT as a function of T_a. The amount of gauche conformation was plotted against the crystalline fraction and the extrapolation of this plot to zero crystalline fraction provided a value of 0.07, suggested that the pure amorphous phase consist of ～ 7% gauche conformation. It was found that the amorphous and crystalline gauche conformation increases at the expense of amorphous trans conformation during thermally induced crystallization of PTT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1497–1504, 2008     

Conformation of some biologically active aromatic ureas

Experimental IR spectroscopic data for the N-H stretching mode frequencies for several types of tri-substituted ureas containing benzyl and/or phenyl substituents as well as theoretical results from B3LYP/6-31G(d,p) computations on selected compounds provide sufficient evidence to determine the conformational state of these molecules. Two types of N-H bands may be found the spectra: (a) A type band due to a classical trans conformation (trans I) of the CONH structure; (b) B type band arising from an alternative trans form (trans II), in which the N-H band is involved in a hydrogen bond like interaction with the aromatic ring at the neighbouring nitrogen atom (benzyl or phenyl substituents). The N-H band of trans ICONH structure is observed at frequencies higher than 3460 cm-1, the actual position depending on weather the non-substituted N-H group is linked to aryl or alkyl substituents. The N-H band of the trans II rotameric structure is observed at 3430-3420 cm-1.     

关于聚丙烯红外光谱中的1157及973厘米-1吸收带

在聚丙烯的红外光谱中,许多作者根据Peraldo对谱带的分析,把1157及973厘米~(-1)吸收带作为全同立构聚丙烯分子螺旋构象的特征吸收,梁诚裕等以阳离子引发(Al(C_2H_5)Cl_2-TiCl_4或AlCl_3)所得“无规”聚合物的光谱中,并无此两吸收带.但是当用阳离子引发丙烯聚合时,会发生异构化反应,得到支化的并在链上有内双键的聚合     

无定型氧化硅转变为α-方石英的振动光谱

红外和喇曼光谱是分子结构信息的重要来源,也是研究表面和催化问题的强有力手段,常用来表征活性中心及吸附物种的结构．为提高稳定性,催化剂一般都要经过焙烧处理,在焙烧过程中,载体结构可能会发生变化,有时还会形成一定的晶相．载体结构变化时,一般会伴随振动光谱的变化,因此在利用振动光谱研究催化体系时,弄清载体的振动光谱是十分必要的．二氧化硅是最常用的催化剂载体之一,但它具有比较多的结构形式,除无定型氧化硅中硅氧四面体可连接成不同的结构外,它还具有石英、鳞石英、方石英等多个晶相系列．对氧化硅的不同结构形式,…     

Experimental evidence for intramolecular blue-shifting C-H...O hydrogen bonding by matrix-isolation infrared spectroscopy

Experimental evidence for intramolecular blue-shifting C-H...O hydrogen bonding is presented. Argon matrix-isolation infrared spectra of 1-methoxy-2-(dimethylamino)ethane exhibit a band at 3016.5 cm-1. Spectral behavior with annealing indicates that this band is assigned to the most stable conformer, trans-gauche-(trans|gauche'), with an intramolecular C-H...O hydrogen bond. Density functional calculations show that this band arises from the stretching vibration of the C-H bond participating in the formation of the C-H...O hydrogen bond. The C-H bond is shortened by 0.004 A, and the C-H stretching band is blue-shifted by at least 35 cm-1 on the formation of the hydrogen bond. The (C)H...O distance is calculated as 2.38 A, which is shorter than the corresponding van der Waals separation by 0.3 A.     

Conformational stability and vibrations of aminopropylsilanol molecule

Density functional theory (DFT), using the B3-LYP/6-31G(d,p) method have been used to investigate the conformation and vibrational spectra of aminopropylsilanetriol (APST) NH2CH2CH2CH2Si(OH)3. The potential function for CCCSi torsion gives rise to two distinct conformers trans and gauche. The predicted energy of the more stable trans conformer is 337 cm-1 less than the energy of gauche conformer. The calculated barriers to the conformation interchange are: 1095, 2845 and 438 cm-1 for the trans to gauche, gauche to gauche and gauche to trans conformers, respectively. For the trans conformer the potential energy curve for the Si(OH)3 groups torsion in APST has been calculated changing the HOSiC dihedral angle. The barrier for the internal rotation of 3065 cm-1 has been obtained. The optimized molecular structure of APST dimer calculated for trans conformer has a SiOSi angle of 143.2 degrees, and a SiOSi bond length of 0.164 nm. A complete vibrational assignment for both conformers as well as for trans-dimer is supported by the normal coordinate analysis, calculated IR intensities as well as Raman activities. On the basis of the results, the vibrational spectra of APST aqueous solution and APST polymer have been analyzed. The average error between the observed and calculated frequencies is 14 cm-1.     

The vibrational spectra and conformations of ethylbenzene

Infrared spectra (4000-250 cm-1) of the liquid, amorphous, crystalline solids and solutions in liquid krypton and Raman spectra (2500-20 cm-1) of the liquid as well as the amorphous and crystalline solids of ethylbenzene and its deuterated analogue-ethylbenzene-d(10) have been recorded. The spectra indicate that in the liquid and amorphous solids a small amount of a second conformer is present, whereas only one conformer remains in the crystalline phases. Assignments of the observed band wave numbers are discussed by comparison with normal mode wave numbers and IR and RS intensities calculated from ab initio 6-31G force fields and optimised geometries for both conformers for two species. All of the normal modes of conformers have been assigned.