ZSM-5沸石上Brönsted酸的红外光谱测定法及改性ZSM-5沸石的表面酸性研究

研究各种 ZSM-5沸石样品的红外光谱发现: 在1875和2000 cm~(-1)附近有两个强红外吸收谱带, 两个谱带吸光度的比值是个特征值。本文提出了以2000 cm~(-1)谱带为“内标”, 用相对吸光度的办法处理ZSM-5沸石的红外光谱, 测定了各种改性ZSM-5样品的Brönsted酸, 并同电位滴定法所测得的Brönsted 酸浓度和异丙苯裂解活性分别关联, 都有较好的对应关系。文中以实验为依据讨论了1875和2000 cm~(-1)谱带的归属, 并根据Beer-Lambert定律, 推导出了相对吸光度与浓度的关系, 从而确立了ZSM-5沸石上红外光谱定量处理方法的理论基础。     

尼龙1010红外光谱的研究

本文研究了尼龙1010的红外光谱。观测了不同热处理样品的红外光谱变化和密度,并测定了拉伸样品的偏振红外光谱。应用因子群解析、简正振动类比,得到许多振动的对称类型、偏振光学性质及选律,进而对尼龙1010的红外光谱谱带做了初步归属,还用电子计算机分峰的方法得到一些新谱带,并就若干谱带展开了讨论.     

ZSM-5沸石上Brnsted酸的红外光谱测定法及改性ZSM-5沸石的表面酸性研究

研究各种 ZSM-5沸石样品的红外光谱发现:在1875和2000cm~(-1)附近有两个强红外吸收谱带,两个谱带吸光度的比值是个特征值。本文提出了以2000cm~(-1)谱带为“内标”,用相对吸光度的办法处理 ZSM-5沸石的红外光谱,测定了各种改性ZSM-5 样品的 Br(?)nsted 酸,并同电位滴定法所测得的 Br(?)nsted 酸浓度和异丙苯裂解活性分别关联,都有较好的对应关系。文中以实验为依据讨论了1875和2000cm~(-1)谱带的归属,并根据 Beer-Lambert 定律,推导出了相对吸光度与浓度的关系,从而确立了 ZSM-5沸石上红外光谱定量处理方法的理论基础。     

天花粉蛋白的化学——Ⅴ.粉末状结晶天花粉蛋白的拉曼光谱

本文报道粉末状结晶天花粉蛋白的拉曼光谱。酰胺Ⅰ和酰胺Ⅲ的振动谱带在1680和1250 cm~(-1)。骨架C_α—C—N的振动谱带在965 cm~(-1)。苯丙氨酸残基的特征谱带在1010和1620 cm~(-1)。酪氨酸残基的特征谱带在845和862 cm~(-1)。色氨酸残基的特征谱带在765 cm~(-1)。酰胺Ⅰ和Ⅲ的谱带中,B折叠和无序结构的特征较为明显。表征无序结构的965 cm~(-1)谱带很弱。     

苯乙烯/甲基丙烯酸甲酯共聚物组分的测定

用红外光谱和紫外光谱进行共聚物组分定量分析时,如果选择的谱带只与共聚物组分含量有关,而与序列结构无关,即可由均聚物的混合物定量分析得到校正工作曲线。共聚物在这些谱带上的吸光度相当于混合物的吸光度。 Kamiyama等人在用IR研究丙烯酸甲酯/苯乙烯(MA/St)共聚物时,发现羰基吸收峰(1730cm~(-1))的半峰高宽度与MA的含量有关;Gallo用UV研究苯乙烯/甲基丙烯酸甲酯(St/MMA)共聚物时发现263毫微米的吸光度和St.组分含量不是线性关系;     

二苄基二硫的晶体拉曼光谱、红外光谱和正则坐标计算

Allum等人~[1]在研究一系列含S—S键化合物的振动光谱时曾给出二苄基二硫在810—400 cm~(-1)范围内的经验谱带指定。本文报道了二苄基二硫的晶体拉曼光谱(40—3100 cm~(-1))和红外光谱(70—3100 cm~(-1)), 在苯与烷烃力场的基础上做了正则坐标计算。综合这多方面的信息, 对于180 cm~(-1)以上的全部红外及拉曼谱带给出了指认。同时对取代苯的力场作了分析讨论。     

单质硫ν_(S-S)伸缩振动的漫反射红外光谱研究

采用傅里叶变换漫反射红外光谱法,在500~400cm~(-1)范围内研究了单质硫S-S键伸缩振动红外吸收模式(νS-S)的一维漫反射红外光谱、二阶导数漫反射红外光谱、四阶导数漫反射红外光谱和去卷积漫反射红外光谱,并针对单质硫νS-S,进一步开展了相关二维漫反射红外光谱研究。结果表明:单质硫νS-S的红外吸收频率主要包括464,466,468,474cm~(-1),而其红外吸收强度的变化顺序为464cm~(-1)474cm~(-1)468cm~(-1)466cm~(-1)。     

聚醚氨酯红外N—H伸缩振动谱带分析

通过快速淬火实验,直接观察到聚醚氨酯中由硬段N—H基与软段—O—形成氢键的N—H伸缩振动谱带位于约3295cm~(-1),低于与硬段本身C=O形成氢键的N—H伸缩振动谱带(约3330cm~(-1))。这两种氢键键连的N—H伸缩振动谱带的位置从聚醚氨酯-四氢呋喃溶液的红外光谱得到证实。在此基础上讨论了三种聚醚氨酯试样的红外光谱中N—H伸缩振动谱带的差异。     

聚酰胺与稀土离子相互作用的研究

用热分析和傅里叶变换红外光谱法研究了尼龙6与稀土离子之间的相互作用。实验结果表明,当将稀土离子引入尼龙6体系后,可观察到以下几种效应：1)尼龙6的熔点显著降低。2)红外光谱结果表明,尼龙6-稀土体系熔化过程中,代表N－H伸缩振动的酰胺A带发生红移。3)尼龙6的酰胺Ⅰ和Ⅱ带区段,可观察到代表与稀土配位的酰胺基团的知,随着温度升高,尼龙6的酰胺Ⅰ,Ⅱ带吸光度降低而在1600cm^-^1附近的新峰的吸光度增加。     

青蒿素和类似过氧化合物的过氧基团振动频率的确认

青蒿素(arteannuin)是中药青蒿中抗疟的有效成分,它是一种含有过氧基团的新型倍半萜内酯,在红外光谱中的强吸收谱带831,881,1115cm~(-1)为过氧基团的特征振动频率.Philpotts等对870cm~(-1)附近的强红外吸收谱带为过氧基团振动频率曾提出疑点,特别是叔过氧基团化合物,它在800～900cm~(-1)范围内产生的强谱带归属于一C—O—基团的振动.而且过氧基团两侧取代基结构不同也将影响谱带的改变,拉电子基团会导致振动频率的波数增大,而推电子基团则使频率向低波数位移.本文用激光拉曼光谱并辅以红外光谱进行研究,比较了700～900cm~(-1)各谱带的谱型,相对强度和退偏振比等数据,并排除了倍半萜环振     

DENSITY, EQUILIBRIUM HEAT OF FUSION AND EQUILIBRIUM MELTING TEMPERATURE OF NYLON 1010

The density, equilibrium heat of fusion and equilibrium melting temperature of Nylon 1010 were determined by means of infrared spectrum, differential scanning calorimetry, wide angle X-ray diffraction and density measurement techniques. According to Starkweatber' s method crystalline density ρ_c and amorphous density ρ_a were estimated to be 1.098 and 1.003 g/cm~3 respectively by extrapolating the straight lines of the IR absorbanee against density to zero intensity. Owing to the less intense in absorbance and less sensitive to the change in crystallinity of the amorphors band the thus obtained ρ_c was too low in value. Thereby the value of the ratio ρ_c /ρ_a is far less than generally accepted mean value for most crystalline polymers. Accordingly, traditional X-ray diffraction method was used through determining thc crystalline dimension(a=4.9, b=5.4, c=27.8, α=49°β=77.0°, γ=63.5°), and a rather correct value of ρ_c or the crystal density 1.13 g/cm~3 was obtained. The equilibrium heat of fusion △H_m~0 was estimated to be 244.0 J/g piotting △H_m 's of specimens with different crystallinity against their corre sponding specific volumes _(sp), and extrapolating to completely crystalline condition (_(sp)~c= 1/ρ_c) As to the equilibrium melting temperature T_m~0, because of the easiness of recrystallization of melt crystallized Nylon 1010 specimen, the well-known Hoffman's T_m-T_c method failed in determining this value and an usually rarely used Kamide double extrapolation method was adopted. The so obtained value of T_m~0 487 seems to be fairly reasonable.     

Raman and Wide-Angle X-Ray Diffraction Studies on Molecular Structure,Crystallinity, and Morphology of Uncompatibilized and Compatibilized Blends of High Molecular Weight Polyethylene/Nylon 12

Molecular structure, crystallinity and morphology of uncompatibilized and compatibilized blends of high molecular weight polyethylene (HMWPE) and Nylon 12 were investigated by using Fourier-transform (FT) Raman spectroscopy, wide-angle x-ray diffraction (WAXD), and scanning electron microscopy (SEM). One of the important purposes of the present study is to compare the present results for HMWPE/Nylon 12 with the previously obtained results for high-density polyethylene (HDPE/Nylon 12). Uncompatibilized and compatibilized blends of HMWPE/Nylon 12 with a Nylon 12 content ranging from 10 to 90 wt% at increments of 10 wt% were prepared. The compatibilized polymer blends were prepared by adding a small amount of maleic anhydride (MAH), and SEM images show that the addition of the small amount of MAH (0.5 wt%) yields a marked improvement of dispersion of HMWPE and Nylon 12. To evaluate the crystallinity of HMWPE from Raman spectra, the relative intensities of bands at 1418 and 1129 cm⁻¹ to the intensity of a band at 1000 cm⁻¹ (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) were estimated for all the uncompatibilized and compatibilized blends of HMWPE/Nylon 12. From the comparison of the relative intensities (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) between the uncompatibilized and compatibilized blends of HMWPE/Nylon 12 it was found that when the Nylon 12 content reaches 40 wt% the crystallinity of HMWPE in the compatibilized blends becomes higher than that of HMWPE in the uncompatibilized blends. The uncompatibilized and compatibilized blends of HMWPE/Nylon 12 (50/50) show quite different x-ray diffraction patterns; the compatibilized blend shows a significantly larger orientational effect in the x-ray pattern of HMWPE. It seems that the increase of interaction of MAH-HMWPE with the Nylon 12 matrix leads to the additional crystallinity.     

Rapid Characterization of Wood Pulp Lignin by Fourier Transform Raman Spectroscopy

FT-Raman spectroscopy is used for the rapid measurement of wood pulp lignin. A total of 23 western softwood pulp samples with known kappa numbers (10–38) are used. Each sample is divided into three portions and scanned separately. The integrated area of the lignin band at approximately 1600 cm⁻¹is ratioed against the integrated area of the cellulose bands in the 1200–1010 cm⁻¹region and correlated to known kappa numbers. The measured ratios behave linearly with the kappa number (r= 0.99) and can be reproducibly determined with an error of approximately 2% or less. The data are presented and discussed in view of the potential for at-line analysis of lignin associated with chemical delignification of wood pulp.     

Sensitive detection of beryllium using a fiber optic liquid waveguide cell

The metallochromic chelating agent, Chromazurol S, has been utilized in conjunction with a fiber optic liquid waveguide capillary cell to enable the sensitive detection of beryllium in solution (30 ng l⁻¹ detection limit) and following extraction from a contaminated plexiglas surface (0.5 ng cm⁻² detection limit). The addition of a cationic surfactant, cetylpyridinium chloride, to Chromazurol S at pH 10 in Tris-HCl buffer results in the formation of two bathochromic peaks in the visible spectrum following metal chelation by beryllium. The first absorbance band, at 515 nm, is intermediate in nature, permitting maximal sensitivity for low beryllium concentrations, but diminishing in intensity at concentrations above 100 μg l⁻¹. The second absorbance band, centered at 610 nm, dominates for beryllium concentrations of 100 μg l⁻¹ and above. Experimental conditions including pH, buffer type, additive surfactants, masking agents, and dye concentration were investigated in order to optimize detection sensitivity and selectivity. A fiber optic spectrometer is used with both a liquid waveguide capillary cell and 1 cm cuvette cell, to give a sensitive and broad dynamic range for beryllium detection that capitalizes on both beryllium metal chelate absorbance bands formed under these conditions.     

The conducting polymer electrolyte based on polypyrrole-polyvinyl alcohol and its application in low-cost quasi-solid-state dye-sensitized solar cells

The effect of polypyrrole (PPy) on the polyvinyl alcohol (PVA)-potassium iodide (KI)-iodine (I₂) polymer electrolytes has been investigated and optimized to use in a dye-sensitized solar cell (DSSC). The different weight ratios of PVA: PPy (93: 2, 91: 4, 89: 6, 87: 8, and 85: 10 wt%) polymer electrolytes (PE) were prepared by solution casting. Structural, complex formation and surface roughness of the prepared electrolytes was confirmed by X-ray diffraction, FTIR, and atomic force microscopy (AFM) respectively. Conductivity plots of all polymer films showed increasing trend with temperature and concentration of PPy. The activation energy of the optimized system found to be 0.871 kJ mol^?1. UV-visible spectrum was adopted to characterize the absorption spectra of the material revealed that increase in the absorbance with increasing PPy content and shifting the absorbance maximum towards lower energy. The indirect band gap decreased from 3.78 to 2.14 eV and direct band gap decreased from 3.88 to 2.71 eV. The EIS analyses revealed the lower charge transfer resistance of 3.029 Ω cm² at the interface between CE and PE. The excellent performance was observed in the fabricated DSSCs using PVA (85%)/PPy (10%)/KI (5%)/I₂ polymer electrolyte with a short-circuit current density of 11.071 mA cm^?2, open-circuit voltage of 0.644 V, fill factor of 0.575, and photovoltaic conversion efficiency of 4.09% under the light intensity of 100 mW cm^?2. Hence, the PPy content in polymer electrolyte influences the remarkable performance of low-cost DSSC.     

On the lower excited electronic states of glyoxal

The polarization of both nπ* absorption bands of glyoxal has been measured in a glass matrix of 2-methyltetrahydrofuran by the photoselection method. The second absorption band in the 30 000 cm^?1 region has been assigned to a ¹A_g → ¹B_g nπ* transition. Its intensity is mainly induced by interaction with the solvent. An absorption band at about 43 000 cm^?1 has been ascribed to a charge transfer transition in complexes of glyoxal and 2-MTHF.     

Thin‐Film Infrared Spectroscopy of Acetonitrile

Acetonitrile and [D₃]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH₃CN 2252 cm^?1, CD₃CN 2262 cm^?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD₃CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell.     

Infrarotspektroskopische untersuchungen an metallcupferronaten im bereich 4000-32 cm-1

The preparation and empirical interpretation of the m.i.r. and f.i.r. spectra of the cupferronates of Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Sn²⁺, Pb²⁺ und Bi³⁺ in the range 4000—32 cm^-1 is described. The bands in the range 1700—500 cm^-1 and the C—H valency vibrations can be assigned to vibrations of the pure ligand; differentiation of individual metal chelates in this range is therefore difficult. In contrast, the far i.r. region (below 500 cm^-1) contains many absorption bands (the metal chelate fingerprint region) which differ in position and intensity. The position of the bands with the highest v—M—O character, which can be recognised on the basis of the large metal-dependent frequency shifts, depends linearly on the second ionization potential of the metal atom, except for the Mn and Sn chelates. The relative absorptions, E_M—O/E, of the far i.r. bands of these cupferronates allow classification of the chelates into groups corresponding to the metal—ligand bonding involved (tetrahedral, octahedral and planar). The characteristic value used for this classification (the quotient of the absorption at the M—0 frequency and the absorbance of the strongest remaining band in the far i.r.) covers the range 0.92–2.17 for tetrahedral chelates, and 5.30–6.20 for planar chelates, with the octahedrally coordinated chelates having intermediate values.     

Temperature dependent Raman study of SB → SC transition in liquid crystalline compound N-(4-n-pentyloxybenzylidene)-4′-heptylaniline (5O.7)

Temperature dependent Raman study of C–H in-plane bending mode (～1163 cm^?1 and ～1190 cm^?1) and C–C stretching mode of phenyl ring (～1571 cm^?1 and ～1594 cm^?1) of N-(4-n-pentyloxybenzylidene)-4′-heptylaniline (5O.7) has been done. Vibrational assignment and potential energy distribution (PED) of individual modes have been calculated employing density functional theory (DFT) for the first time. The S_B → S_C transition is nicely depicted in the variation of the linewidth of the ～1163 cm^?1 band and the peak position of ～1594 cm^?1 band with temperature. Because of a small amount of charge density transfer from the core part to the alkyl chain region, the ～1163 cm^?1 band shifts towards lower wavenumber side whereas the ～1190 cm^?1 band towards higher wavenumber side at S_B → S_C transition. The ～1571 cm^?1 and ～1594 cm^?1 bands are assigned as 8a and 8b modes, whose relative intensity variation with temperature gives the evidence of increased possibility of C–H bending motion of the linking group and the C–C stretching of the alkyl chain in S_C phase.     

Multi-component analysis of low-density polyethylene oxidative degradation

The oxidative degradation of polyethylene in various conditions has been studied. In order to gain insight into the oxidation process, a method for the curve-fitting analysis of the IR carbonyl band between 1800 cm⁻¹ and 1600 cm⁻¹ in oxidized low-density polyethylene (LDPE) has been developed. Up to 10 components were needed to fit the band envelope, whose assignments and peak positions were based on the literature and on the synthesis of an appropriate model compound. The determination of the other band parameters, such as peak width and peak shape, necessary for reliable best fitting of the absorbance envelopes, was obtained by overall fitting optimization process. By using the available extinction coefficients, the quantitative determinations of the main oxidized species, i.e. ketones, carboxylic acids, esters, γ-lactones and ketoacids, were obtained with a reasonable confidence by rigorous parameter setting. The method was applied to the IR analysis of LDPE samples oxidized in different conditions (under thermal and irradiation stimulation), either as beads or films, as a function of time. Total hydroperoxide concentrations were also quantitatively estimated by a modified iodometric titration procedure. A good linear correlation between concentrations estimated by chemical titration and by intensity analysis of the free hydroperoxide IR band was observed.