卟啉铜接枝SiO2有机-无机复合材料及强的非线性折射率

通过卟啉配合物Meso-四(4-羧基苯基)卟啉铜(简称Cu(Ⅱ)-TCPP)中的羧基与γ-氨基丙基三乙氧基硅烷(NH₂(CH₂)₃Si(OC₂H₅)₃,KH550)中的氨基的相互化学作用,成功地把卟啉配合物接枝到KH550中,随着KH550中乙氧基的水解与聚合反应的进行,卟啉铜连接到固体介质中,从而大幅度提高了卟啉在无机固体介质中的掺杂浓度. 将反应产物与γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(CH₂CHCH₂O(CH₂)₃Si(OCH₃)₃,KH560) 相杂化,形成物化性能良好、连接卟啉的有机-无机复合材料. 用红外光谱表征了Cu(Ⅱ)-TCPP与KH550的化学反应产物,用紫外—可见吸收光谱研究Cu(Ⅱ)-TCPP的分子状态. 应用Z扫描技术研究不同Cu(Ⅱ)-TCPP掺杂浓度的复合材料的非线性光学性质,其三介非线性折射率n₂达-1.1161×10^-16 m²/W. 关键词： 非线性折射率 有机-无机复合材料 接枝 Meso-四(4-羧基苯基)卟啉铜     

Preparation of microparticles composed of cinnamoyl gelatin and cinnamoyl alginate by spray-drying method and effect of UV irradiation and pH value on their release property

Microparticles composed of cinnamoyl gelatin (CinGel) and cinnamoyl alginate (CinAlg) were prepared as a UV irradiation- and pH-responsive carrier by a spray-drying method. CinGel and CinAlg were prepared by a condensation reaction. Using a colorimetric method, the gelatin to CA mass ratio and the alginate to CA mass ratio were calculated to be 1:0.04 and 1:0.02, respectively. The complexation of CinGel and CinAlg in aqueous solution took place when the medium was acidic (e.g., pH 4.0) and the maximum complexation was obtained when the CinGel/CinAlg mass ratio was 7:3. On SEM photographs, some spray-dried CinGel/CinAlg particles were spherical and others were irregularly shaped, and the diameter was a few to tens of micrometers. The release degrees of amaranth loaded in UV-treated microparticles were lower than those of the dye loaded in UV-untreated ones, possibly because of the photo cross-linkage of CinGel and CinAlg. Regardless of whether the microparticles were UV-treated, the release degree at pH 4.0 was significantly lower than the release degree at pH 6.0 and pH 8.0, possibly because of complexation of CinGel and CinAlg under the acidic condition.     

PROTON NUCLEAR MAGNETIC RESONANCE AND ELECTRON PARAMAGNETIC RESONANCE INVESTIGATION OF α-α CROSS-LINKED Fe-Co HYBRID HEMOGLOBINS

The following asymmetric α1 99 Lys-α2 99 Lys cross-linked Fe(Ⅱ)-Co(Ⅱ) hybrid hemoglobins (Hbs) were first prepared from derivatives of hemoglobin C (β6 Glu-Lys) and human normal HbA: [α(Co)β(Fe)]A[α(Co)β(Co)]cXL, [α(Fe)β(Co)]A[α(Co)β(Co)]cXL, etc.Their 500 MHz 1H NMR and EPR spectra were measured in order to study the change in their tertiary and quaternary structure under atmosphere of deozy, oxy and carbon monoxide (with or without IHP). From the change of T and R marks in 1H NMR hydrogen bonding region, it is proved that oxygen molecules are first bonded to α(Fe) subunits rather than to β(Fe). The experimental phenomena provided further evidence that intermediate states of ligation are present in addition to T and R state during process of binding of oxygen to Hb. IHP facilitates transformation of T state to R state. The same conclusion can also be drawn from the results of EPR spectra at 77 K.