湖泊藻类叶绿素-α和悬浮物浓度的高光谱定量遥感模型研究

本文利用地物光谱仪对太湖水体进行了光谱测量和同步采样分析，对获得的数据尝试用光谱分离法进行分析，从中分离出蓝藻和悬浮物的特征波峰，建立波峰高度与同步水质采样得到的叶绿素-α浓度和悬浮物浓度的对应关系，得出其遥感定量反演算法，并实际应用在OMIS成像光谱仪图像上．     

人工光合作用反应中心的研究进展

本文对几种人工光合作用反应中心系统,做一个简单的综述,其中包括叶绿素和细菌叶绿素二聚体,卟啉二聚体,卟啉-苯醌共价键络合物以及其他合成中心。     

Semiempirical PM5 molecular orbital study on chlorophylls and bacteriochlorophylls: comparison of semiempirical, ab initio, and density functional results

The semiempirical PM5 method has been used to calculate fully optimized structures of magnesium-bacteriochlorin, magnesium-chlorin, magnesium-porphin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), and d, and bacteriochlorophylls a, b, c, d, e, f, g, and h with all homologous structures. Hartree-Fock/6-31G* ab initio and density functional B3LYP/6-31G* methods were used to optimize structures of methyl chlorophyllide a, chlorophyll c(1), and methyl bacteriochlorophyllides a and c for comparison. Spectroscopic transition energies of the chromophores and their 1:1 or 1:2 solvent complexes were calculated with the Zindo/S CIS method. The self-consistent reaction field model was used to estimate solvent shifts. The PM5 calculations predict planar structure of the porphyrin ring and central position of the four coordinated magnesium atoms in all pigments studied, in accord with the experimental, ab initio, and density functional results, a significant improvement as compared to the older semiempirical PM3 approach. Only small differences in PM5 and B3LYP/6-31G* or Hartree-Fock/6-31G* minimum energy geometries of the reference molecules were observed. Calculations show that in 1:1 solvent complexes, where the magnesium atom is five coordinated, the magnesium atom is shifted out of the plane of the porphyrin ring towards the solvent molecule, while the hexa coordinated 1:2 complexes are again planar. The PM5 method gives atomic charges that are comparable with those obtained from the Hartree-Fock/6-31G* and B3LYP/6-31G* calculations. The single point ZINDO/S CIS calculations with PM5 minimum energy structure gave excellent correlations between calculated and experimental transition energies of the chlorophylls and bacteriochlorophylls studied. Such correlations may be used for prediction of transition energies of the chromophores in protein binding sites. Calculations also predict existence of dark electronic states below the main Soret absorption band in all chromophores studied. The results suggest that the semiempirical PM5 method is a fairly reliable and computationally efficient method in predicting molecular parameters of porphyrin-like molecules.     

叶绿素及其Cu、Zn衍生物的伪装性能研究

研究了类叶绿素活性颜料在伪装应用中的光谱性能及光稳定性问题。从绿色植被的色素着手,分析了叶绿素的性质及影响其降解的原因,用Cu2+、Zn2+金属离子替代天然叶绿素中的Mg2+,制备了叶绿素衍生物,并通过光谱特性和光稳定性对叶绿素衍生物的特性进行了比较分析。研究结果表明,从光谱性能和稳定性两方面综合考虑,Cu叶绿素更适合作为叶绿素修饰目标来提高颜料的稳定性,从而为新型光学伪装涂料的制备提供材料基础。     

Hydroxymethylated Phyllobilins: A Puzzling New Feature of the Dioxobilin Branch of Chlorophyll Breakdown

Colorless nonfluorescent chlorophyll (Chl) catabolites (NCCs) are formyloxobilin‐type phyllobilins, which are considered the typical products of Chl breakdown in senescent leaves. However, in degreened leaves of some plants, dioxobilin‐type Chl catabolites (DCCs) predominate, which lack the formyl group of the NCCs, and which arise from Chl catabolites by oxidative removal of the formyl group by a P450 enzyme. Here a structural investigation of the DCCs in the methylesterase16 mutant of Arabidopsis thaliana is reported. Eight new DCCs were identified and characterized structurally. Strikingly, three of these DCCs carry stereospecifically added hydroxymethyl groups, and represent bilin‐type linear tetrapyrroles with an unprecedented modification. Indeed, DCCs show a remarkable structural parallel, otherwise, to the bilins from heme breakdown.     

内陆水体叶绿素a含量定量检测的研究

以武汉东湖为实验基地,通过对其水体的多次检测,获得了从2006年6月到9月4个月的东湖水体透射光谱,并与蒸馏水透射光谱进行比较,对东湖水富营养化程度进行了定性分析.采用一种新的测量方法得到叶绿素a浓度与677 nm和703 nm处相对强度的差值和比值有很好的线性相关性,建立了东湖水体叶绿素a含量的准确定量检测模型,为实现对东湖水实时、快速、准确监测提供了基础,为高精度遥感水质分析提供了参考.     

Fine Tuning of Chlorophyll Spectra by Protein‐Induced Ring Deformation

The ability to tune the light‐absorption properties of chlorophylls by their protein environment is the key to the robustness and high efficiency of photosynthetic light‐harvesting proteins. Unfortunately, the intricacy of the natural complexes makes it very difficult to identify and isolate specific protein–pigment interactions that underlie the spectral‐tuning mechanisms. Herein we identify and demonstrate the tuning mechanism of chlorophyll spectra in type II water‐soluble chlorophyll binding proteins from Brassicaceae (WSCPs). By comparing the molecular structures of two natural WSCPs we correlate a shift in the chlorophyll red absorption band with deformation of its tetrapyrrole macrocycle that is induced by changing the position of a nearby tryptophan residue. We show by a set of reciprocal point mutations that this change accounts for up to 2/3 of the observed spectral shift between the two natural variants.     

油莱中叶绿素的提取及稳定性

研究了浸提法提取油菜叶绿素的最佳工艺条件及稳定性。结果表明,浸提法的最佳提取工艺条件为：以无水乙醇为提取剂,料液比为1：10（g／mL）,在70℃下提取4h。叶绿素在近中性或偏碱性介质环境中性质基本稳定,随着氧化剂浓度的增加其分解程度不断加大,且其光稳定性降低。     

流动注射-抑制化学发光法测定克百威

基于在碱性介质中,克百威抑制鲁米诺-过氧化氢-叶绿素铜钠体系的化学发光,提出了流动注射-抑制化学发光法测定克百威含量的方法。试验结果表明:叶绿素铜钠对克百威荧光猝灭过程是静态猝灭过程,叶绿素铜钠与克百威结合形成物质的量比为1比1的稳定配合物,平衡常数(K0)为3.41×105L.mol-1(25℃),结合距离(r)为0.39 nm。克百威质量浓度在0.08～2.00 mg.L-1范围内与其发光强度呈线性关系,方法检出限(3σ/k)为0.03 mg.L-1。此法用于克百威杀虫剂样品的分析,测得方法的平均加标回收率为101.5%。     

Two-photon spectroscopic behaviors and photodynamic effect on the BEL-7402 cancer cells of the new chlorophyll photosensitizer

The spectroscopic properties of a new chlorophyll derivate photosensitizer(CDP) are studied under the excitation wavelengths at 800 and 400 nm using femtosecond pulses from a Ti:sapphire laser.The damaging effect of CDP on the BEL-7402 cancer cells is also investigated upon two-photon illumination at 800 nm.The normalized fluorescence spectra of CDP in tetrahydrofuran(THF) show that two-photon and one-photon spectra have the same distributions and the same emission bands(675 nm).The life-times of two-and one-photon induced fluorescence of this molecule are of the order of 5.0 ns.By comparing the data it is shown that there is some difference between the two lifetimes,but the differ-ence is less than one nanosecond.The two-photon absorption cross section of the molecule is also measured at 800 nm and estimated as about σ′2 ≈ 31.5×10-50 cm4·s·photon-1.The results of two-photon photodynamic therapy(TPPDT) tests show that CDP can kill all of the tested cancer cells according to the usual Eosine assessment.Our results indicate that the two-photon-induced photophysical,photo-chemical and photosensitizing processes of CDP may be basically similar to those of one-photon ex-citation.These behaviors of the sample suggest that one may find other possible methods to estimate some photosensitizers' effects in details such as their distribution in cells and the reactive targets of the sub-cellular parts of some tumor cells via two-photon excitation techniques.