A novel method for determination of polyester end-groups by NMR spectroscopy

An efficient, convenient and quantitative method for characterising polyester end-groups is described. We have found that trichloroacetyl isocyanate (TAI) reacts rapidly and quantitatively with both carboxyl [C(O)OH] and hydroxyl (OH) chain ends to form derivatives that can be readily determined by ¹H NMR spectroscopy. The TAI capped end-groups give rise to characteristic imidic NH resonances in a normally clear region of the ¹H NMR spectrum [δ∼10-11.5 for C(O)-O-C(O)-NH-C(O)CCl₃ from C(O)OH, δ∼8-9 for O-C(O)-NH-C(O)CCl₃ from OH]. The method has been successfully applied to quantitative determination of the end-groups of a wide variety of oligomeric polyesters. It has also been applied to higher molecular weight polyesters including commercial, bottle grade, poly(ethylene terephthalate) (PET) and PET based copolyesters (e.g. PETG).     

新型超微晶软磁合金FePCCuMoSi微观结构缺陷的正电子湮没研究

用正电子湮没方法研究了新型超微晶软磁合金的微观结构缺陷，样品选用的是在不同温度下退火的Ｆｅ８１Ｐ１２Ｃ３Ｃｕ１Ｍｏ０．５Ｓｉ２．５合金，结果表明，合金的微观结构构陷大小，密度随退火温度有规律地变化，这种现象可能与非晶的晶化过程有关。     

电子束、离子束与蓝宝石相互作用的研究

研究了电子束、离子束作用于Al2O3表面时成分的变化，表明无论电子束或离子束都能使Al2O3发生分解，产生导电的元素Al。实验在PHI610·SAM上进行，电子束轰击下（3keV，O．5μA，入射角60°）10s就有元素Al分解出来，2min以后就达到饱和，分解析出量随时间成a（1－e－bt）的关系。离子束轰击下同样发生元素Al的分解，但当Ei＞3keV时，由于剥离速率加大，溅射5min时表面Al峰反而比1min时要弱。这时表面Al含量处于分解析出与溅射剥离的动态平衡中。实验还发现了Al2O3的解析与表面成分有关（如碳的含量）。最后讨论电子束与离子束的解析机理。     

四种别藻蓝蛋白三聚体的时间分辨荧光光谱研究

研究了从Ａｎａｂａｎａｖａｒｉｂｉｌｉｓ中提取的４种别藻蓝蛋白ＡＰＣＩ，ＡＰＣＩＩ，ＡＰＣＩＩ及ＡＰＣＢ三聚体的稳态光谱和皮秒荧光光谱。采用Ｍｏｎｔｅ－Ｃａｒｌｏ方法对瞬态荧光光谱进行拟合，实验结果表明：ＡＰＣＩ荧光有两个带，其中第一个带位于６６２ｎｍ，有两个时间组分：３５．８ｐｓ和１．６７ｎｓ；第二个带位于６８０ｎｍ，有两个时间组分：３４．２ｐｓ和１．６４ｎｓ；ＡＰＣＩＩ瞬态荧光位于６６０ｎｍ，有两个时间组分：２０．４ｐｓ和１．６４ｎｓ；ＡＰＣＩＩ瞬态荧光位于６６０ｎｍ，有两个时间组分：２３．８ｐｓ和１．７６ｎｓ；ＡＰＣＢ瞬态荧光有两个带，其中第一个带位于６６２ｎｍ，有两个时间组分：３６．６ｐｓ和１．４５ｎｓ；第二个带位于６８０ｎｍ，有两个时间组分：２５．８ｐｓ和１．６２ｎｓ。实验结果一方面说明了藻胆体核内４种别藻蓝蛋白形成能量传递的两条途径；另一方面瞬态荧光解叠结果揭示了ＡＰＣＩ和ＡＰＣＢ三聚体内能量传递的超快过程。     

Selective catalytic reduction of nitric oxide by propane over vanadia-titania aerogels

An investigation has been carried out of the effect of vanadia loading on the activity and selectivity ofV₂O₅TiO₂ aerogel catalysts, prepared by a two-step procedure, for the reduction of NO by propane. The structure of catalysts have been characterized by laser Raman spectroscopy and XRD measurements. At vanadia loading levels below ca. 4.4 wt%, the vanadia is present in the form of coordinated polymeric species, whereas crystallites of V₂O₅ are formed at higher vanadia contents. At this critical level of 4.4 wt% V₂O₅, the kinetic measurements showed also a maximum in the activity per mass of catalyst which very likely indicated that the coordinated polymeric surface species are more active than crystalline V₂O₅. The selectivity towards the formation of dinitrogen decreased as the loading increased, presumably because of the formation of larger polymeric species and V₂O₅ crystallites, below and above the critical loading level, respectively. For the reduction of NO by propane, titania supported vanadia aerogel catalysts are significantly more active, per mass of catalyst, and more selective towards N₂ formation than conventionalV₂O₅TiO₂ and V₂O₅Al₂O₃ aerogel catalysts, at vanadia loading levels below ca. 11 wt%.     

氮化钛薄膜的高分辨AES谱和XPS谱研究

着重讨论了TiNx薄膜俄歇电子谱的定量分析方法和X射线光电子谱中线形的变化。利用已知组元强度定量分析技术和Ti的LMV俄歇电子峰，探讨TiNx薄膜中N含量的定量方法。由该方法给出的定量结果与X射线光电子谱定量结果相一致。同时，利用X射线光电子谱测定了TiN和Ti2N2p轨道的结合能。并针对Ti2p峰形随N含量的变化，给出新的解释。     

Growth of Fe on Si (100) at room temperature and formation of iron silicide

Low-energy electron diffraction (LEED), Auger electron spectroscopy and X-ray photoelectron spectroscopy (XPS) investigations of both the growth of an iron film on silicon (100) at room temperature and the subsequent formation of iron silicide are the subjects of this paper. An in-situ cleaned silicon (100) wafer without carbon or oxygen contamination exhibiting the known 2 × 1 reconstruction in the LEED pattern served as the substrate. Iron was deposited on this reconstructed surface at 300 K. The comparison of theoretical calculations based on three growth mechanisms with XPS data obtained with take-off angles of 0° and 50° clearly demonstrates a layer-by-layer growth of the iron film on silicon (100). At 300 K no formation of iron silicide was observed, although an interaction between iron and silicon could be detected at the interface. The formation of iron silicide was observed at annealing temperatures of 630–730 K. Quantitative XPS analysis yields the presence of FeSi₂, when the thickness is large enough. Neither the iron film on silicon nor the silicide shows any LEED pattern.     

Subsurface structures in initial stage of FeSi2 growth studied by high-resolution Rutherford backscattering spectroscopy

The initial stage of iron silicide formation is investigated by high-resolution Rutherford backscattering spectroscopy. During the Fe deposition on Si(001) at 470 °C, the formation of FeSi₂ is confirmed by the surface peak analysis. Initially, FeSi₂ grows epitaxially so that one of the major crystallographic axes is parallel to the <111> axis of the Si substrate. With increasing Fe deposition, the deviation between the major crystallographic axis of the silicide region and Si<111> increases although the electron diffraction pattern is independent of the amount of Fe deposition. Therefore, the subsurface crystallographic structure of iron silicide is transformed from a cubic-like to a low-symmetry structure.     

In-situ ESR spectroelectrochemical studies of overoxidation behaviour of poly(3,4-butylenedioxythiophene)

The behaviour of poly(3,4-butylenedioxythiophene) (PBuDOT), a relative of poly(3,4-ethylenedioxythipohnene) PEDOT within the poly(3,4-alkylenedioxythiophene) family, has been investigated at potentials above its electrochemical stability threshold using in situ ESR spectroelectrochemistry. The aim was to investigate the effect of electrochemical overoxidation on the charge carrying species, namely polarons, normally generated and annihilated during reversible redox doping and dedoping reactions, by determining the potential dependencies of spectroscopic parameters of the ESR spectra of the polymer over a selected potential range. Specific features of the trends of these dependencies allowed also for an evaluation of presence of the second type of charge carrying species—diamagnetic bipolarons and the effects of their interactions with polarons at different potentials. Around 1.5 V, where the boundary of electrochemical stability of the polymer lies, sharp drop of the concentration of paramagnetic centres has been observed together with a transitory narrowing of the ESR line. These changes were found to be irreversible as evidenced by the course of subsequent reduction half-cycle, which differed from the one for a not overoxidised polymer, observed in previous studies. Aided by the results of electrochemical studies it was concluded that the overoxidation process leads to a degradation of the polymer most probably due decrease of the conjugation length of the main chain π-bond through cross-linking or addition reactions. While the electrochemical results pointed to a non-complete degradation of the polymer, the specific parameters of the ESR line in the reduction half-cycle indicate that the remaining spins are confined to isolated segments of a partially degraded polymer where their behaviour resembles oligomer-like radicals.     

Structural Description of Polyaromatic Nucleus in Residue

The proton nuclear magnetic resonance spectroscopy （1H-NMR）, the synchronous fluorescence spectrometry （SFS） and the ruthenium ions catalyzed oxidation （RICO） method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction （BIPH）, the cata-condensed fraction （CATA）, the peri-condensed fraction （PERI） and the condensed index （BCI） were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.