丙硅乳液的核磁共振研究

单介绍了²⁹Si NMR实验技术;用²⁹Si NMR测定了丙硅乳液原料羟基硅氧烷的平均聚合度、平均分子量、平均羟基含量;用¹³C NMR分析了丙硅乳液的结构组成。     

笼形倍半硅氧烷NMR的研究

笼形倍半硅氧烷是一类典型的多面体有机-无机分子复合物. ²⁹Si NMR是测定这类含硅化合物结构的有效方法. 利用²⁹Si NMR对6种笼形八聚倍半硅氧烷的结构进行了研究,结合所得数据探讨了这类化合物中取代基电负性对²⁹Si NMR化学位移的影响.根据¹H,¹³C NMR数据及各峰归属可以进一步判断笼形倍半硅氧烷取代基R的类型和结构.     

煅烧高岭土的NMR研究

采用²⁹Si、²⁷Al MAS NMR谱对不同产地高岭在同一煅烧温度及同一产地高岭土在不同煅烧温度的煅烧产物进行了研究. 实验结果表明：不同产地高岭土在同一煅烧温度煅烧产物的²⁹Si MAS NMR相似,²⁷Al MAS NMR谱有所区别,煅烧温度对煅烧产物的²⁹Si、²⁷Al MAS NMR有一定影响.     

靶向新药吉非替尼的核磁共振波谱研究

应用1D、2D NMR实验技术（¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HMQC、¹H-¹³C HMBC等）研究了靶向新药吉非替尼的结构,对其1H NMR和¹³C NMR谱峰作了全归属,并讨论了F原子对吉非替尼的¹H、¹³C NMR的影响.     

南海海绵Dysidea fragilis中两个倍半萜内酯的NMR研究

用一维¹H、¹³C NMR谱、DEPT ¹³C NMR谱、选择性远程DEPT ¹³C NMR、¹H-¹H COSY和¹³C-¹H COSY二维核磁共振技术研究了南海海绵Dysidea fragilis中的两个倍半萜herbadysidolide(1)和furodysinin lactone(2),确认了化学结构,并对其¹³C NMR和¹H NMR谱进行了归属.药理活性试验表明:1和2具有一定的心血管活性.     

Lasiodonin Acetonide的NMR数据解析

对lasiodonin acetonide进行了¹H和¹³C NMR检测,参考lasiodonin, maoecrystal T, wikstroemioidin B和rabdocoetsin A的¹H、¹³C NMR数据,通过DEPT和¹H-¹H COSY、HSQC、HMBC等2D NMR技术对该化合物所有的¹H和¹³C NMR信号进行了全归属和详细解析.     

苯基哌嗪衍生物的NMR波谱研究

通过¹H NMR、¹³C NMR、及HMBC、HSQC、¹H-¹H DQFCOSY等2D NMR方法对新合成的10个苯基哌嗪衍生物类抗高血压药物进行结构鉴定, 并对这些化合物的¹H NMR和¹³C NMR信号进行了全归属. 初步探讨了取代基对分子¹³C化学位移的影响.      

卢立康唑的波谱学特征和结构确证

用红外吸收光谱、紫外吸收光谱、核磁共振（NMR）波谱（包含¹H NMR、¹³C NMR、DEPT135、¹H-¹H COSY、¹H-¹³C HMQC和¹H-¹³C HMBC）、质谱、差示扫描量热分析、X-射线粉末衍射和元素分析等方法对卢立康唑进行了结构分析.对卢立康唑所有的¹H和¹³C NMR信号进行了归属,并通过多种谱学技术确证了卢立康唑的结构.     

盐酸马尼地平的核磁共振数据解析

盐酸马尼地平是第三代合成降压新药．本文利用一维、二维核磁共振（NMR）技术,包括¹H NMR、¹³C NMR DEPT-135、¹H-¹H NOESY、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC,对其¹H和¹³C NMR信号进行了全归属,进一步确证了其分子结构．同时,对其¹H NMR和¹³C NMR谱中一些异常信号进行了讨论．     

硼替佐米的波谱学数据解析

对抗肿瘤药硼替佐米的紫外吸收光谱（UV）、红外吸收光谱（IR）、电喷雾离子源-质谱（ESI-MS）、核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）数据进行了解析,对其¹H和¹³C NMR谱峰进行了全归属,通过多种谱学技术确证了硼替佐米的结构.     

聚丙烯腈热裂解产物的ESR和固体13C NMR研究

用电子自旋共振(ESR)和固体¹³C NMR研究了聚丙烯腈(PAN)在不同裂解温度(T_P)下的结构变化,当T_P从250℃增加到600℃,ESR信号线形没有变化,g值与T_P无关,ΔH_PP减小,自旋浓度(N_S)开始增加,T_P进一步升高,N_S又减少.¹³C NMR谱指出在不同T_P下谱峰发生很大变化,与另文报道的红外及X-射经衍射结果一致,随T_P升高,PAN逐渐脱去小分子形成具有环化共轭结构的产物.     

NMR方法在煤炭分析中的应用进展

简要介绍了核磁共振（NMR）方法在煤炭组成及热解过程分析中的应用. 目前用于煤炭分析的NMR方法主要包括固体NMR和液体NMR. 从检测手段来看,以¹³C NMR和¹H NMR方法较多,¹⁵N NMR, ¹⁹F NMR和³¹P NMR也在煤炭的分析中发挥了重要作用. 其中用于区分和选择性检测不同官能团的NMR谱编辑方法的发展, 进一步推进了NMR在煤炭化工中的应用.     

On the rank-dependence of coal tar secondary reactions

The secondary reactions of volatile compounds, including coal tar and light gases, accounts for a great portion of soot formation and the subsequent heat release and pollutant emissions in the combustion zone. While coal primary pyrolysis has been extensively studied over the last few decades and several network pyrolysis models has been developed to describe this process, coal secondary pyrolysis is still not well understood. The Babcock and Wilcox Company has been investigating coal secondary pyrolysis in order to develop a comprehensive mechanism for inclusion in predictive computational fluid dynamics and coal combustion models. Supportive experiments were carried out in an entrained-flow reactor. Tar was extracted from the pyrolysis byproducts of seven coals of widely-distributed rank at temperatures ranging from 923 to 1473 K, and analyzed by ¹³C NMR. Tars formed from higher rank coals generally demonstrated higher sooting propensities. This rank-dependent sooting propensity is associated with tar’s chemical structure properties. With increased heat treatment severity, tar molecules lose a substantial amount of aliphatic attachments, and the average size of substitution per cluster decreases. Compared to tars formed from high-rank bituminous coals, those formed from low-rank sub-bituminous coals have a larger attachment portion, higher averaged substitution, and higher oxygen-containing functional groups. These differences contribute to the higher cracking propensity observed for low-rank coal tars.     

Biomorphous SiC ceramics prepared from cork oak as precursor

Porous ceramic materials of SiC were synthesized from carbon matrices obtained via pyrolysis of natural cork as precursor. We propose a method for the fabrication of complex-shaped porous ceramic hardware consisting of separate parts prepared from natural cork. It is demonstrated that the thickness of the carbon-matrix walls can be increased through their impregnation with Bakelite phenolic glue solution followed by pyrolysis. This decreases the material’s porosity and can be used as a way to modify its mechanical and thermal characteristics. Both the carbon matrices (resulted from the pyrolysis step) and the resultant SiC ceramics are shown to be pseudomorphous to the structure of initial cork. Depending on the synthesis temperature, 3C-SiC, 6H-SiC, or a mixture of these polytypes, could be obtained. By varying the mass ratio of initial carbon and silicon components, stoichiometric SiC or SiC:С:Si, SiC:С, and SiC:Si ceramics could be produced. The structure, as well as chemical and phase composition of the prepared materials were studied by means of Raman spectroscopy and scanning electron microscopy.     

Method of calculating the phase composition of SiC–Si–C materials obtained by silicon infiltration of carbon matrices

The synthesis of SiC–Si–C materials by siliconizing porous carbon matrices has been considered, and a method of determining their phase composition has been devised. Preforms of two types have been siliconized, i.e., biomorphic carbon matrices prepared by wood pyrolysis and artificial porous graphites prepared by mixing and compacting carbon powders with an organic binder. The calculated phase compositions are in good agreement with microstructure metallographic examination data.     

Linear expansion coefficient of the SiC/Si biomorphic composite

In the temperature range 100–650 K, the linear expansion coefficient β was measured for the SiC/Si biomorphic composite, a new cellular ecoceramic fabricated from a porous cellular carbon matrix prepared through pyrolysis of wood (white eucalyptus) in an argon ambient with subsequent infiltration of molten Si into the channels of the matrix and the formation of 3C-SiC. The SiC/Si samples studied had an “excess” ～30% volume concentration of Si and a porosity of ～13–15%. The measurements were conducted on samples cut along (β_∥) and across (β_⊥) the tree growth direction. The measured values of β(T) of SiC/Si are compared with literature data available for the linear expansion coefficients of Si and 3C-SiC.     

辐照和碳化对SiC空心微球的影响

以聚碳硅烷(PCS)为原料,通过炉内成球技术制备SiC空心陶瓷微球,讨论辐照交联和高温碳化对SiC陶瓷微球化学成分、成键结构和表面特性的影响。结果表明,PCS在热处理过程中的失重率约为35%,其分解温度在400~800℃之间。微球经电子束辐照后会生成以Si—C—Si和Si一O一Si骨架结构为主的三维网络交联结构。碳化过程使Si—C_32键,Si—H键和C—H键断裂,生成以Si—C为主的无定形态Si(C。辐照的均化作用使高温热处理碳化的微球能够维持完好的球壳结构,且具有更好的表面粗糙度和平整性。     

Electrical and thermoelectric properties of the SiC/Si biomorphic composite at high temperatures

The electrical resistivity ρ and the thermopower coefficient α of a SiC/Si biomorphic composite fabricated from a porous carbon matrix [prepared through pyrolysis of wood (white eucalyptus)] by infiltrating molten Si into the empty channels of the matrix were measured in the temperature ranges 100–950 and 100–750 K, respectively. Silicon reacts chemically with the carbon of the matrix to produce 3C-SiC, which, in combination with the excess Si unreacted with carbon, forms the SiC/Si biomorphic composite. The SiC/Si samples studied had a concentration of “excess” Si of ～30 vol % and a porosity of ～13–15 vol %. Measurements of ρ were carried out on samples cut either along (ρ_∥) or across (ρ_⊥) the tree growth direction, and α was measured on a sample cut along the tree growth direction.     

Thermal and electrical properties of a white-eucalyptus carbon preform for SiC/Si ecoceramics

The thermal conductivity κ and electrical resistivity ρ of a white-eucalyptus cellular carbon preform used to fabricate silicon-carbide-based (SiC/Si) biomorphic ceramics have been measured in the 5-to 300-K temperature interval. The carbon preform was obtained by pyrolysis (carbonization) of white-eucalyptus wood at 1000°C in an argon ambient. The κ(T) and ρ(T) relations were measured on samples cut along the tree growth direction. The experimental data obtained were processed.     

The Effect of ZrO2 Interphase on Interfacial Frictional Stresses in SiC/ZrO2/SiCf Composites

Two types of SiC fiber tows (Hi-Nicalon? and Hi-Nicalon S?) were coated with stabilized ZrO₂ and composited using preceramic polymer impregnation pyrolysis to form SiC/SiC_f minicomposites. Properties of the fiber/matrix interface in composites were investigated using the indentation method in which a pyramidal indenter was used to push on an individual fiber and cause sliding at the interface. The interfacial frictional stresses were determined from the force–displacement relation. The composites reinforced by the ZrO₂-coated fibers have smaller interfacial frictional stresses than composites reinforced by the initial fibers and show fibers sliding relatively more easily with respect to the SiC matrix.