Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Interdiffusion of hydroxyl groups and of doping additions between a bearing pipe and a deposited layer in billets of fiber light guides

Using Raman spectroscopy, a quantitative analysis of the distribution of OH⁻ ions on the boundary between a bearing pipe and a glass layer deposited from chlorides in billets for quartz fiber light guides is carried out. Water penetrated into the light-reflecting shell to a depth of several tenths of a millimeter, depending on the composition of the doping layer (i.e., ultimately on the temperature of the depsoition process). A. F. Ioffe Physical-Technical Institute, Academy of Sciences of Russia, 26, Politekhnicheskaya St., St. Petersburg, 194021, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 548–550, July–August, 1997.     

转动喇曼散射截面的群论计算

本文利用群链U(4)U(3)O(3)描述双原子分子N_2和O_2振转谱的对称性质,并利用群论方法计算了N_2和O_2分子转动喇曼散射的跃迁矩阵元,给出了它们的转动喇曼散射的截面。结果与实验较好地符合。     

利用喇曼光谱测量氧碘化学激光器氯气利用率的实验研究

 介绍了利用自发喇曼散射光谱测量氧碘化学激光器单态氧发生器氯气利用率的原理及实验装置，并给出了在以氮气作为稀释气的0.1mol/s射流式氧发生器上测试的结果，测试相对误差小于12%。由于该方法只需要通过测量喇曼谱线相对强度之比，即可算出氯的利用率，因此不需要另外的标定实验，从而避免了因标定带来的影响。该方法减小了测试误差，简化了实验过程，提高了测试效率。     

Electronic structure and vibrational spectra of cis-diammine(orotato)platinum(II), a potential cisplatin analogue: DFT and experimental study

Orotic acid (vitamin B₁₃) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C₅H₂N₂O₄)(NH₃)₂] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin.     

掺杂对碳纳米管拉曼光谱及场发射性能的影响

采用高温热解法在860℃分别制备出了镓、氮以及硼和氮掺杂的碳纳米管,提纯后利用丝网印刷工艺分别将它们制备成薄膜,并测试了它们的拉曼光谱与场发射性能。测试结果表明,掺杂纳米管的缺陷密集度比纯碳纳米管明显增大,而它们的场致电子发射性能则与掺杂元素的性质密切相关。镓和氮掺杂的纳米管均具有非常优异的场发射性能,而硼和氮共掺杂的纳米管的场发射性能很差。掺杂引起碳纳米管费米能级附近能态密度的变化及功函数的降低是其具有优异场致电子发射性能的主要原因。     

Raman spectroscopic study of ceramic Sr2Bi4Ti5O18

Raman spectra of ceramic Sr2Bi4Ti5O18 （SBTi5） are reported to consist of four different Raman bands. Temperature-dependent spectra reveal the relationship between the lattice vibration and the material＇s structure. There appears a relatively large change in structure of the material at about 273K, The anharmonic potential of the material has a great influence on its phonon mode full width at half maximum （FWHM）, which can be expressed by a function of temperature. Theoretical fittings of the FWHMs for the two modes at around 312 cm^-1 and 464cm^-1 indicate that the latter phonon mode is more anharmonic than the former one.     

环境光对PE塑料薄膜近红外激光拉曼光谱的影响

探讨了环境光自然光和室内荧光灯光的存在,对PE透明塑料薄膜的近红外激光拉曼光谱的影响.研究表明不同的环境光,会对近红外拉曼光谱产生不同的明显特征峰.自然光干扰产生的是以倒峰群形式为主,而室内荧光灯光造成的干扰主要以尖锐的脉冲峰形式.虽干扰表现形式不同,但都有严重地影响,在测定时一定要引起重视,不能忽略.建议在进行透明塑料近红外拉曼光谱检测时,须在暗室或暗罩遮光保护中进行,以完全隔离环境光的影响.     

现场拉曼光谱研究乙腈在金电极上的解离吸附行为

利用共焦显微拉曼系统、结合合适的电极表面粗糙方法研究了非水体系 0 1mol/LLiClO4 /CH3CN溶液中 ,乙腈分子在金表面的吸附和解离行为。结果表明非水体系中乙腈可在金表面发生还原反应 ,产物CN- 离子与电极表面作用形成的表面配合物可在较宽的电位区间吸附于电极表面。溶液中的微量水、激光照射以及电极电位均对该反应有较大的影响。通过拉曼谱图的比较得出乙腈分子解离出的CN- 在金电极表面比在银电极表面有更强的吸附作用。     

Nd:LuVO_4晶体的拉曼光谱研究

采用不同的几何配置测量了Nd:LuVO4晶体的室温拉曼光谱,根据群论对称性分类计算了该晶体的红外和拉曼活性振动模并与实验结果做了比较,指认了测定的特征谱线。测量并分析了Nd:LuVO4晶体A1g全对称类的高温拉曼光谱,讨论了拉曼频移随温度变化的关系,认为晶体的热膨胀是引起拉曼频移变化的主要原因。