Orientational Ordering of the Near-Surface Layers of Nitrobenzene

Two types of absorption centers, one being related to monomers and the other to dimers, have been revealed by the method of statistical analysis of the normalized absorption spectra of a superthin interlayer of nitrobenzene of variable thickness formed on activated surfaces of quartz and barium fluoride and measured for different thicknesses of the interlayer. On a decrease in the interlayer thickness the concentration of dimers increases.     

Precise synthesis of porphyrin array scaffolding polyisocyanides

Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006     

过氧化物模拟酶在介体型生物传感器方面应用初探

meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)～1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。     

钴-5,10,15,20-四(3-甲氧基-4-羟基苯基)卟啉修饰玻碳电极的L-抗坏血酸化学传感器研究

将水合 5,10,15,20-四-(3-甲氧基-4-羟基苯基)钴卟啉(CoTMHPP)修饰在玻碳电极表面,制成CoTMHPP修饰电极.电极稳定性好且灵敏度高,对抗坏血酸有良好的电催化氧化作用,测定线性响应范围为1.0×10(-5)～1.0×10(-2)mol/L,响应时间小于12s.本文研究了电极的性质和应用,并用于药物中抗坏血酸的测定,其测定结果与碘量法一致.     

meso-四(对烷氧苯基)卟啉金属配合物的合成和性能研究(IV)

合成了系列卟啉乙酸合锰配合物9个,其中6个为未见文献报道的新化合物.用UV,1HNMR,IR,MS,元素分析等表征确证了配合物的结构,总结了锰与卟啉类配体配合的IR,UV,1HNMR判据.采用差示扫描量热法(DSC)和偏光显微镜(PM)研究了该系列配合物的液晶性能,发现8个配合物具有液晶性.考察了烷氧基链长、配位金属离子和分子空间结构对液晶性能的影响.     

Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for speciation analysis of volatile and non-volatile compounds of nickel and vanadium in crude oil

A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L⁻¹ Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g⁻¹, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test.     

meso－四（4－磺酸苯基）卟啉与Co（Ⅱ）的显色反应的研究

本文研究了弱酸性介质中钴（Ⅱ）与ＴＰＰＳ４的显色反应条件。实验发现胺类化合物质子化后，不参与成络反应，而均能使ＴＰＰＳ４试剂的吸光度大大降低，从而提高了测定的灵敏度，Ｃｏ（Ⅱ）－ＴＰＰＳ４络合比为１：１，ε＿（４２６）＝３．５４×１０￣５，钴含量在０～５．０μｇ／２５ｍＬ范围内呈线性，并用于烟草、茶叶中痕量钴的测定，得到了满意的结果。     

Thermodynamic Insight into the Origin of a Calix[n]arene-[60]fullerene Interaction and its Application to a Porphyrin-[60]fullerene Energy Transfer System

The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra.     

哌嗪取代卟啉的合成、表征及其抗癌活性

设计并合成了6个具有抗癌活性的哌嗪取代卟啉化合物,分别为5,10,15,20-四[4-(4'-乙基哌嗪基)苯基]卟啉(TEPPH2,8a),5,10,15,20-四[4-(4'-丁基哌嗪基)苯基]卟啉(TBPPH2,8b),5,10,15,20-四[4-(4'-庚基哌嗪基)苯基]卟啉(THPPH2,8c),5,10,15,20-四[4-(4'-苯基哌嗪基)苯基]卟啉(TPhPPH2,8d),5-[4-(4'-乙基哌嗪基)苯基]-10,15,20-三苯基卟啉(EPTPPH2,8e)和5-[4-(4'-丁基哌嗪基)苯基]-10,15,20-三苯基卟啉(BPTPPH2,8f).这些卟啉化合物都由取代苯甲醛与吡咯缩合而成,每一个卟啉分子中含有一个或四个具有抗癌活性的取代哌嗪结构,结构经元素分析,MS,1H NMR,IR和UV-vis等表征.初步的生物活性研究表明,这些化合物具有一定的抗癌活性,因而在医学上可能具有潜在应用前景.     

Synthesis and polymerisation of α,ω-bis(3-pyrrolyl)alkanes

The synthesis, characterisation and polymerisation studies of a homologous series of α,ω-bis(pyrrolyl)alkanes are described. These α,ω-bis(pyrrolyl)alkanes were produced using Friedel-Crafts acylation followed by reduction of the carbonyl group using Red-Al^®. Chemical polymerisation of the resultant dimers using FeCl₃ produced poly(α,ω-bis(pyrrolyl)alkane) films, which were characterised by SEM, FTIR and tested for conductivity.