二茂钛含氟有机酸衍生物的质谱研究

本文研究了二茂钛含氟长链有机酸衍生物(1～3)和具有环状结构的新型二茂钛全氟有机酸(4～7)的电子轰击质谱(EIMS)和负离子化学电离质谱(NICIMS)。在EI谱中出现弱的或不出现M~+,1～7均以CpTiF_2离子为基峰。高质量区的主要特征碎片离子有[M-·cp]~+、[M-R]~+(1～3)和氟重排离子。在低质量区出现一系列二茂钛及茂钛氟重排离子。 1、4～7的NICI(CH_4)质谱中,4、5出现强的M~-离子峰,1出现[M-1]-离子峰,有两个钛的环状结构化合物6和7出现双电荷M~=离子峰,而不出现M~-。     

COMPUTER SIMULATION OF A SINGLE POLYMER CHAIN IN DIFFERENT SOLVENTS

In the present paper, the behavior of a single polymer chain under various solvent conditions was modeled by self-avoiding walks (SAW) with nearest neighbors attraction Δε on a simple cubic lattice. Determination of the θ-condition wasbased on the numerical results of the mean square radius of gyration and end-to-end distance. It was found that at the θtemperatue Δε/kT equals -0.27. The exponents a in the Mark-Houwink equation with different interaction parameters areconsistent with the results of experiments: under θ-condition, a = 0.5, and for a good solvent α= 0.74-0.84, respectively.     

Detection of metalloproteins in human liver cytosol by synchrotron radiation X-ray fluorescence combined with gel filtration chromatography and isoelectric focusing separation

Synchrotron radiation X-ray fluorescence (SRXRF) spectroscopy is an advanced method of quantitative multielemental analysis with space resolution of several microm and sensitivities in the microg g(-1) range. It can be used for keeping track of trace elements after an electrophoretic separation of biological samples. In this paper, proteins in human liver cytosol were separated with gel filtration chromatography and thin layer isoelectric focusing (IEF). The contents of metal ions in protein bands were determined by SRXRF. The results showed that in the molecular weight (MW) range of 10 approximately 25 kDa, there were at least 2 Zn-containing bands with isoelectric point (pI) of 5 approximately 6 and 6.2 approximately 7, respectively and about 11 Fe-containing proteins with pI of 4.4, 4.6, 4.8, 5.0, 5.2, 5.3, 5.5, 5.6, 6.6, 6.8, and 7.2, respectively, present in human liver cytosol. The Zn-containing band with pI of 5-6 is the dominant species of zinc in this MW range. In addition, the Cu-containing bands with pI of 5.0 and below 4.8 were also detected. It is demonstrated that the procedure could be widely used in further investigations of the chemical species of trace elements in biological samples.     

Development of high-performance liquid chromatographic fingerprints for distinguishing Chinese Angelica from related umbelliferae herbs

A high-performance liquid chromatographic (HPLC) fingerprint of Chinese Angelica (CA) was developed basing on the consistent chromatograms of 40 CA samples (Angelica sinensis (Oliv.) Diels). The unique properties of this HPLC fingerprints were validated by analyzing 13 related herbs including 4 Japanese Angelicae Root samples (JA, A. acutiloba Kitagawa and A. acutiloba Kitagawa var. sugiyame Hikino), 6 Szechwan Lovage Rhizome samples (SL, Ligusticum chuanxiong Hort.) and 3 Cnidium Rhizome samples (CR, Cnidium officinale Makino). Both correlation coefficients of similarity in chromatograms and relative peak areas of characteristic compounds were calculated for quantitative expression of the HPLC fingerprints. The amount of senkyunolide A in CA was less than 30-fold of that in SL and CR samples, which was used as a chemical marker to distinguish them. JA was easily distinguished from CA, SL and CR based on either chromatographic patterns or the amount of coniferyl ferulate. No obvious difference between SL and CR chromatograms except the relative amount of some compounds, suggesting that SL and CR might have very close relationship in terms of chemotaxonomy. Ferulic acid and Z-ligustilide were unequivocally determined whilst senkyunolide I, senkyunolide H, coniferyl ferulate, senkyunolide A, butylphthalide, E-ligustilide, E-butylidenephthalide, Z-butylidenephthalide and levistolide A were tentatively identified in chromatograms based on their atmospheric pressure chemical ionization (APCI) MS data and the comparison of their UV spectra with those published in literatures.     

An unusual mixed-valence Cu(I)-Cu(II) 3-D framework

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.     

Effect of Pluronic F127 on the pore structure of macrocellular biodegradable polylactide foams

Thermally induced phase separation technique was utilized to fabricate biodegradable poly(l ‐lactic acid) (PLLA) macrocellular foams which were capable of being applied in tissue engineering. The block copolymer Pluronic F127 composed of (polyethyleneoxide)‐(polypropyleneoxide)‐(polyethyleneoxide) [(PEO)‐(PPO)‐(PEO)] was used as a porogen. Water/dioxane mixtures with different volume ratios were used as solvents. The addition of Pluronic F127 could induce an appearance of large pores (50–200 μm) besides small pores (10–20 μm) or a change from a solid–liquid phase separation to a liquid–liquid phase separation. The role of Pluronic F127 depends on the water/dioxane ratios in the PLLA/dioxane/water system. The X‐ray diffraction patterns and porosity measurement results showed that Pluronic F127 was crystallized and existed on the pore wall. The effect of Pluronic F127 on changing pore structure is attributed to the occurrence of the interaction of the lipophilic PPO blocks in Pluronic F127 with PLLA clews, consequently, this results in PLLA aggregation and early phase separation on cooling. Copyright © 2004 John Wiley & Sons, Ltd.     

酚氧桥联的不对称双铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成和磁性

本文合成了一组新的不对称双核配合物「Cu(samen)Cu(terp)」和「Cu(samen)Zn(terp)」,samen~4和terp分别表示N N’-乙二水杨酰胺胺根阴离子和2.2′:6′2″-联三吡啶。配合物「Cu(samen)Cu(terp)」的变温磁化率已测,其数值用最小二乘法与Bleancy-Bowers方程拟合,求得交换积分J=-0.538cm~(-1),表明配合物中铜离子间有极弱的反铁磁自旋交换作用。     

Self aggregation of binary mixtures of sodium dodecyl sulfate and polyoxyethylene alkyl ethers in aqueous solution

The mixed micelles of sodium dodecyl sulphate (SDS) with Brij35 and Brij 97 were studied separately by fluorescence measurement using pyrene as fluorescent probe. In the range of 0–1.0 mole fraction (X) of added SDS to Brij solutions, the cmc value of the mixed micelles varies from 0.085 to 8 mmol with Brij 35 and 0.04 to 8 mmol with Brij 97. The aggregation number also changes. A measure of the stability of mixed micelles is also presented. The interaction parameter ₁₂ and the chain–chain contribution parameter (B₁) are extracted from the analysis of the results. This parameter B₁ is related to the standard free energy change associated with the introduction of one ionic species into a nonionic micelle coupled with the release of one nonionic species from the micelle. The clouding behaviour of Brij 97 in the presence of SDS was investigated and the associated thermodynamic parameters of clouding were generated and discussed.     

Polymer lateral diffusion at the solid-liquid interface

Measurements are presented of how polymer surface diffusion at the solid-liquid interface is controlled by surface coverage. The method of measurement was fluorescence correlation spectroscopy (FCS), and the system was poly(ethylene oxide) (PEG) adsorbed onto methyl-terminated self-assembled monolayers in buffered aqueous solution. The translational diffusion coefficient at first increased with increasing surface concentration, presumably because the number of adsorption sites per molecule decreased. Ultimately it slowed by 1 order of magnitude, presumably reflecting jamming by neighboring chains.