w-十一烯酸表面改性纳米碳酸钙粒子反应机理的差示FTIR光谱研究

采用差示傅里叶变换红外光谱(FTIR)法对w十一烯酸表面改性的纳米碳酸钙粒子的组成进行了测试,结果发现:在其差谱上,波数位于1 572,1 542 cm-1附近出现了较明显的(RCC)2-Ca离子的特征吸收带,波数位于912,3 078 cm-1附近分别出现了端双键上C-H的面外弯曲(γCH)和伸缩振动(νCH)吸收带,波数位于1 746,1 703 cm-1附近分别出现了酯羰基和羧羰基的特征吸收带.由此推测,改性剂与纳米碳酸钙表面作用机理可能是:改性剂的端羧基与纳米碳酸钙表面的钙离子结合,形成(RCOO)2-Ca离子键,从而在纳米碳酸钙表面接枝上带有端双键的活性有机基团;同时,纳米碳酸钙表面利用氢键作用吸附微量有机基团.这些有机基团共同缠绕在纳米碳酸钙表面,提高了纳米碳酸钙在无水乙醇中的分散性.     

小鼠近死亡期皮肤损伤活性的FTIR光谱研究

应用傅里叶变换红外(FTIR)光谱分析研究了近死亡期皮肤损伤活性差异。生前5 min组,死后5 min组,正常组的FTIR光谱的峰形、峰高有明显差异：(1)与脂类有关的3 007和1 745 cm-1谱带的峰高,生前伤比死后伤增强。(2)与碳水化合物相关谱带1 160 cm-1的峰高,生前伤比死后伤明显升高。(3)1 640 cm-1谱带为蛋白质相关的酰胺Ⅰ带,损伤组峰高要低于正常组,生前伤中最低。这一结果表明,FTIR光谱分析技术有望成为法医近死亡期皮肤损伤活性判定的有效方法。     

红细胞内吞银包金纳米颗粒的实时表面增强喇曼研究

研究了结晶紫包裹的银包金纳米粒子进入红细胞的实时过程.利用激光光镊喇曼技术每隔20s通过光镊囚禁红细胞并收集该细胞及邻近溶液的喇曼光谱,抽取光谱中具代表性的特征峰来观察其强度随时间的变化.结果表明:从囚禁的红细胞中收集到的光谱包括了归属红细胞与结晶紫的特征峰.红细胞的光谱特征峰1 001、1 128、1 213cm-1和结晶紫的光谱特征峰915、1 177、1 389、1 586、1 619cm-1的强度随着时间增加,表明在红细胞与纳米粒子共培养的过程中,纳米粒子在红细胞中累积,并引起红细胞信号增强.分析红细胞与其邻近溶液的光谱差,发现归属结晶紫的光谱特征峰913、1 179、1 586cm-1随时间呈类余弦的变化,表明红细胞内的结晶紫包裹的银包金纳米粒子含量先升高后降低再升高.通过计算得到纳米粒子开始进入红细胞的时间范围及进入的速度、被溶酶体降解的速度.研究表明表面增强喇曼技术为研究外物进入细胞提供了新的实验方法和思路.     

纳米磷化镓粉体中混杂石墨和金刚石微晶的拉曼光谱分析

利用Raman光谱并结合能量色散X射线显微分析(EDX)和X射线衍射图谱(XRD)对混杂于纳米磷化镓粉体内的石墨和金刚石纳米微晶进行了分析。结果表明,在纳米GaP粉体Raman光谱中,位于1324 cm-1和1572 cm-1的两个宽强散射谱带分别归属于金刚石的F2g模和石墨的E2g模振动。EDX结果证实纳米GaP粉体材料中含有碳元素。XRD图谱中出现了石墨和金刚石的低晶面指数衍射峰。     

固体丙氨酸变温过程的二维相关红外分析

采用傅里叶变换红外光谱法 (FTIR)和二维相关分析 (2Dcorrelationanalysis)技术研究了固态丙氨酸的变温过程。结果表明 :固体丙氨酸从室温 2 0℃加温至 15 0℃ ,随着温度的升高 ,红外谱峰的位置和谱峰的相对强度变化不明显 ,除CCN反对称伸缩振动红移了 5个波数以外 ,其余各谱峰平均仅位移了 1～ 2个波数。借助于二维相关分析 ,在 15 70～ 16 5 0cm-1范围内 ,丙氨酸分别出现了 16 2 5和 15 89cm-1两个自动峰 ,16 2 5cm-1处的自动峰较强 ,即NH 3 随温度升高变化较突出 ,其热敏程度较大 ;而 15 89cm-1处的自动峰相对较弱 ,说明COO-随温度升高变化较小。同时二维相关分析还进一步揭示了丙氨酸的结构变化首先以NH 3 为主导 ,然后相应引起CH ,CH3 ,COO-各官能团结构的变化规律。为固态粉末丙氨酸脱氢氧化机理的研究提供了一个重要的理论依据。     

胆囊癌的傅里叶变换红外光谱研究

运用衰减全反射(attenuated total reflection,ATR)探头与傅里叶变换红外(Fourier transform infra-red,FTIR)光谱仪,测定并分析了新鲜离体的胆囊癌组织18例和良性组织139例的FTIR光谱。结果表明:(1)胆囊癌的1 167和1 123 cm-1谱带的峰位显著地向低波数移动(P0.05),而1 309 cm-1谱带的峰位显著地向高波数移动(P0.05)。(2)胆囊癌组织光谱多个峰的相对强度I2 856/I1 461,I1 167/I1 461,I1 123/I1 461和I1 082/I1 461明显升高(P0.05)。(3)1 167和1 082 cm-1谱带的半高宽显著升高(P0.05),谱带1 461 cm-1的半高宽则显著降低(P0.05)。(4)癌组织1 750 cm-1谱带的出现几率明显增加(P0.05)。与胆囊良性组织相比较,癌组织光谱中与脂类、糖和核酸相关的谱带均发生了明显的变化。     

氨基酸在银胶溶液中的表面增强拉曼效应

文章报道了通过制备合适的银胶盐纳米溶液 ,得到的甘氨酸、缬氨酸和赖氨酸在银胶溶液中的表面增强拉曼光谱。低波数 2 38cm-1谱带的出现 ,表明氨基酸分子已与银表面产生明显吸附。在所得SERS图谱中 ,表征C—C基团的 90 0～ 930cm-1谱带、表征NH2 基团的 110 0cm-1左右谱带和表征COO-基团的14 0 0cm-1附近的谱带振动都得到显著加强 ,其原因主要是通过羧基基团及氨基基团与银粒子表面产生吸附 ,增强机制属于化学增强 ,为短程效应。本实验中 ,当银胶溶液 pH值降低时 ,对拉曼散射的增强效果影响不大。     

内吞金纳米粒子的鼻咽癌细胞SERS光谱

采用内吞方法将金纳米粒子引入细胞内,测试分析单个活性CNE-1鼻咽癌细胞的常规拉曼光谱和SERS光谱,并对其进行初步谱峰归属。CNE-1细胞的常规拉曼光谱有6个主要的拉曼峰:718,1001,1123,1336,1446和1660cm-1;沉积于细胞内的金纳米粒子强烈地增强了细胞内生化物质拉曼信号,在内吞金纳米粒子的CNE-1细胞的拉曼光谱中出现了20多个SERS拉曼信号,主要拉曼峰的强度明显高于常规拉曼信号。DNA骨架振动(1026,1097,1336和1585cm-1)证明金纳米粒子通过内吞作用而进入细胞核内。结果表明,基于胶体金SERS技术可能为活性鼻咽癌细胞内生化物质的探测提供一种高灵敏的方法。     

辉石巨晶结构OH的分子光谱结晶学定向初探

利用分子光谱谱带位移、谱带强度、谱带形态等的变化,可以初步对晶体作结晶学定向。普通辉石结构OH红外光谱3组谱带值,垂直c轴方向相对于平行c轴的谱带各不相同：第一组谱带值,3 629～3 633 cm-1谱带红移到3 601～3 616 cm-1;第二组谱带值3 514～3 543 cm-1同样有红移现象;第三组3 460～3 465 cm-1的谱带值相反则有蓝移现象。相对强度上,两个方向上第一组的谱带强度相当;第二组、第三组谱带强度平行方向明显强于垂直方向。形态上则差别不大。拉曼谱垂直方向谱带强度普遍强于平行方向,谱带位置与形态基本不变。结构OH不同结晶方向的谱图性质可以反映一定的地质构造环境。     

变温红外光谱法研究左旋丙交酯(L-LA)的结晶相关谱带

变温红外光谱法是研究结晶化合物结晶谱带的一种有效方法。作者合成了左旋丙交酯,采用红外光谱仪、核磁共振仪、热分析仪表征了样品的结构与性能;然后利用红外变温法在15～120 ℃范围内对左旋丙交酯做了变温研究。结果发现当T=95 ℃时丙交酯在770～800 cm-1区域有两条吸收谱带变化明显,样品退火后,变化的两谱带又基本复原,由此推测,此两谱带与左旋丙交酯的结晶相关联,可能是其结晶相关谱带。     

Electronic States of Difluorocarbene Calculated by Multireference Configuration Interaction Method

We investigate the geometries and energies of seven electronic states X~1A_1,A~1B_1,a~3B_1,B~1A_2,b~3A_2,C~1B_2and c~3B_2 of CF_2 carbene using internally contracted multireference configuration interaction methods including Davidson correction(icMRCI+Q) with different basis sets aug-cc-pVXZ(X=T,Q,5).For the first time,the potential energy curves of electronic states of CF2 related to the lowest dissociation limit are calculated at the icMRCI+Q/aug-cc-pVTZ level.The ab initio results will further increase our understanding of the structures and dynamics of electronic states of CF_2 radical.     

二氧化锡气敏纳米粉体的红外光谱研究

采用溶胶-凝胶法制备了纳米级SnO2,利用XRD和IR光谱对其晶化过程进行了详细研究。结果表明,硝酸胶溶有利于SnO2纳米晶的生成,676和545cm-1处的红外吸收分别为二氧化锡中Eu型对称的Sn-O的伸缩振动和A2u型对称的O-Sn-O变角振动,且随着纳米粉体热处理温度的升高,峰形窄化,A2u型的变角振动峰强度降低。     

Effect of Dispersion of Carbon Black on Electrical and Thermal Properties of Poly(Ethylene Terephthalate)/Carbon Black Composites

A type of grafted carbon black (GCB), prepared with a low molecular weight antioxidant compound by in-situ reaction, was dispersed in poly(ethylene terephthalate) (PET) by a melt-blending process. Dispersion of fillers, volume resistivity, and thermal properties were investigated using scanning electron microscopy, a high-resistance meter, differential scanning calorimetry, and thermogravimetric analysis, respectively. The results show that, compared with carbon black (CB) particles, GCB particles dispersed better in the PET matrix, whereas the conductivity percolation threshold of PET/GCB was higher than that of PET/CB. The addition of GCB or CB elevated the cold crystallization temperature of PET, reflecting the effectiveness of carbon fillers as nucleating agents. But carbon fillers decreased the crystallization enthalpy of PET during both heating and cooling process. Both CB and GCB elevated the starting temperature of thermal degradation of PET and increased the amount of residues for the composites over that of neat PET.     

The Nucleation Effect of Grafted Carbon Black on Crystallization of Poly(Ethylene Terephthalate)/Grafted Carbon Black Composite

Poly(ethylene terephthalate)/grafted carbon black (PET/GCB) and poly(ethylene terephthalate)/carbon black (PET/CB) composites were prepared by melt blending. The nucleating effect of CB and GCB were investigated using differential scanning calorimetry (DSC) analysis. The morphologies of the spherulites in PET, PET/CB and PET/GCB composites were observed by means of scanning electron microscopy (SEM). All results showed that GCB had higher nucleating activity than CB in PET and PET/GCB composite had higher rate of nucleation and crystallization. The melting behaviors of neat PET, PET/CB and PET/GCB composites after non‐isothermal crystallization were investigated as well. It was evident that the melting behavior of PET is greatly influenced by addition of CB and GCB.     

Investigation of the Morphological and Mechanical Properties of Polyethylene Terephthalate (PET)/Ethylene Propylene Diene Rubber (EPDM) Blends in the Presence of Multi-Walled Carbon Nanotubes

In this study the blends of polyethylene terephthalate (PET)/ethylene propylene diene rubber (EPDM) in the presence of multi-walled carbon nanotubes (MWCNT) (1 and 3?wt %) were prepared by melt compounding in an internal mixer. Mechanical and morphological properties of the nanocomposites were investigated. The thermal behaviors of the PET/EPDM nanocomposites were also investigated, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of the mechanical tests showed that the tensile strength, elastic modulus and the hardness of the blends were increased with increasing CNT, while the impact strength and elongation at break decreased. The DSC and TGA results showed an increase of melting temperature (T_m) and degradation temperature of the nanocomposites with the addition of the carbon nanotubes, because the carbon nanotubes serve both as nucleating agents to increase T_m and prevent the composite from degradation to increase the thermal stability. The microstructure of the composites was evaluated through field emission scanning electron microscopy (FESEM) and the results showed a good distribution of the MWCNT within the polymer blend.     

Sorption and decomposition of crude oil using exfoliated graphite/ZnO composites

Exfoliated graphite/ZnO composites (EG/ZnO) were prepared by impregnating expandable graphite with Zn(OH)₂, abruptly expanding at 700 °C for 40 s, and heating at 500 °C for 3 h. The composites were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), nitrogen adsorption and mercury porosimetry. The sorption capacity of the composites for spilled crude oil was measured and under UV irradiation the decomposition of the absorbed crude oil was investigated. The results showed that the composites provided with the adsorption and photocatalysis capacity for crude oil at the same time. The sorption capacity of the composites decreased gradually on increasing the ZnO content of the composites. Moreover, the decomposition ratio of the absorbed crude oil increased on increasing the ZnO content or decreasing the weight ratio of crude oil to composites.     

Registration temperature effect in polymers: Physico-chemical aspects

Registration temperature effect in two different polymers - poly(ethylene terephthalate) (PET) and polypropylene (PP) films - is investigated. Temperature effects on track formation are considered in terms of molecular mobility and relaxation transitions. The track eth rate is measured as a function of irradiation temperature in the range of 77 to 373 K. The obtained results are compared with the radical yields, radiothermoluminescence curves and thermally stimulated currents measured with the aim of detecting changes in the mobility of macromolecules and radiolysis intermediates. It is found that the change of the track etch rate with changing registration temperature correlates with γ- and glass transitions in PP and with β-and glass transitions in PET.     

H2Se(X1A1)分子的解析势能函数

使用密度泛函B3LYP方法和 6-311++G**基组,在优化H2Se(X1A1)基态结构,确定其正确离解极限,计算所有两体项和三体项参数基础上,建立了H2Se(X1A1)的多体项展式解析势能函数。其中对处于激发态两体项HSe(A2∑+)的计算,则使用SAC-CI方法。H2Se(X1A1)的等值势能图准确地表现了其结构和势能面的特征。     

Latent-Crimp Behavior of PET/PTT Elastomultiester and a Concise Interpretation

The latent-crimp behavior of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) elastomultiester was investigated by comparing the crimp state before and after annealing at different temperatures. Both the work of crimp extension and the work of crimp retraction in a multicycle tensile-recovery action are introduced to characterize the crimp transition. The variations of the work with the number of cycles and the ultimate work ratio were analyzed by a nonlinear fitting method to find some relation with the annealing temperature, and the morphological changes of the crimp were observed. The governing mechanism for crimp development was also studied by contrasting the shrinkage behaviors of PET/PTT, with PET and PTT single-component filaments. Two criteria were applied to determine the optimum temperature for PET/PTT to fully develop its crimp, and the results were only slightly different. Finally, isothermal shrinkage kinetic measurements were also performed to find a proper annealing duration for PET/PTT at an optimum temperature.     

非金属晶体导热系数与压力和温度相关性

 讨论了非金属晶体的导热系数k与压力p和温度T的相互关系。从理论上导出了低压和低温下的两个实验拟合关系式，即K_T=A+Bp和k_p＝A₁+B₁/T，其中A、B、A₁、B₁为拟合常数。计算结果与实验结果符合得非常好。此外，还讨论了k在高压、高温及冲击压缩下的响应。