Synthesis and Photophysical and Electrochemical Study of Tyrosine Covalently Linked to High‐Valent Copper(III) and Manganese(IV) Complexes

As bio‐inspired chemical model of the oxygen‐evolving complex (OEC) in photosystem II, a new tyrosine‐modified corrole ligand 3 and its high‐valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of 1a and 2a . The corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at ?0.17 and 0.77 V vs. Ag/Ag⁺, respectively.     

卟啉作为信号传递介质的紫外可见光谱研究

合成了6种氨基酸水杨醛席夫碱(Sal-AA)：Sal-Gly(甘氨酸)、Sal-Phe(苯丙氨酸)、Sal-Arg(精氨酸)、Sal-Tyr(酪氨酸)、Sal-Met(甲硫氨酸)、Sal-Glu(谷氨酸)及其金属铜配合物。并分别在2种不同介质(三氯甲烷和甲醇)中，与四苯基卟啉TPP进行反应，研究了其紫外可见光谱性质，讨论了卟啉作为人工信号转导体系的传递介质，与氨基酸水杨醛席夫碱铜配合物的反应中，实现信号分子铜离子进一步传递的可能性以及溶剂对该信号传递的影响。结果表明，在三氯甲烷为溶剂时，除了Sal-Met的铜配合物之外，其余均能被TPP夺取而形成Metal TPP。而在以甲醇为溶剂时，只有Sal-Gly的铜配合物能被TPP所夺取。     

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores

Gold nanoparticles have been conformally coated with amorphous silica (using a sol-gel method) and then an organic polymer (via surface-grafted, atom transfer radical polymerization) to form spherical colloids with a core-double-shell structure. The thickness of silica and polymer shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the reagent and/or the reaction time. Selective removal of the silica layer (through etching in aqueous HF) led to the formation of hollow polymer beads containing movable gold cores. This new form of core-shell particles provides a unique system for measuring the feature size and transport property associated with hollow particles. In one demonstration, we showed that the thickness of a closed polymer shell could be obtained by mapping the electrons backscattered from the core and shell. In another demonstration, the plasmon resonance band of the gold cores was used as an optical probe to follow the diffusion kinetics of chemical reagents across the polymer shells.     

A novel method of the separation/preconcentration and determination of trace molybdenum(VI) in water samples using microcrystalline triphenylmethane loaded with salicyl fluorone

It is the first time that triphenylmethane was used as an adsorbent to preconcentrate and separate trace amount of molybdenum in water samples. The effects of different parameters, such as acidity, stirring time and various metal ions, the amounts of triphenylmethane and salicyl fluorine, etc. on the enrichment yield of molybdenum have been studied to optimize the experimental conditions. Under the optimum conditions, molybdenum can be adsorbed on the surface of microcrystalline triphenylmethane loaded with salicyl fluorone by the intermolecular action strength. The possible reaction mechanism for the enrichment of molybdenum was discussed in detail in this paper. Mo(VI) can be completely separated from Pb(II), Co(II), Cu(II), Cr(III), Ni(II), Hg(II), Zn(II), Cd(II), Fe(III) and Al(III) in the solution. The proposed method was successfully applied to the determination of trace amount of molybdenum in various water samples by spectrophotometry after preconcentration using microcrystalline triphenylmethane. The preconcentration factor is from 83 (500 ml water sample was enriched to 6.0 ml) to 166 (1000 ml water sample was enriched to 6.0 ml). The detection limit is 1.3 × 10⁻⁵ mg l⁻¹ and the linearity is maintained in the concentration range 3.8 × 10⁻³ to 0.36 mg l⁻¹ with a correlation coefficient of 0.9998. The recoveries are in the range of 93.5-104%. The relative standard deviation is 1.8-2.9%. Analytical results obtained with this novel method are very satisfactory.     

电化学检测在流动注射分析中的应用

评述了近几年来电化学检测在流动注射分析中的应用，展望了流动注射电化学分析法的发展动向。     

西印度蔗螟聚集信息素次要组份合成方法的改进

2-甲基-4-庚醇和2-甲基-4-辛醇是西印度蔗螟(Metamasiushemipterus)聚集信息素的次要组份，本文以天然产物(S)-亮氨酸为原料合成出了2-甲基-4-庚醇及2-甲基-4-辛醇的所有对映异构体，其关键步骤是由(2S)-4-甲基-1,2-戊二醇合成出(2S)和(2R)-4-甲基-1,2-环氧戊烷两种重要中间体，目标产物光学纯度可达95%以上。     

Self-assembly, optical behavior, and permeability of a novel capsule based on an azo dye and polyelectrolytes

A novel capsule composed of an azo dye, Congo red (CR), and different polymers, including poly(styrenesulfonate, sodium salt) (PSS), poly(allylamine hydrochloride) (PAH), and poly(diallyldimethylammonium chloride) (PDDA), have been successfully fabricated by the layer-by-layer self-assembly technique. The stepwise linear deposition process was monitored by means of UV-visible absorption measurements. The formation of hollow capsules was verified by confocal laser scanning microscopy (CLSM) and scanning force microscopy (SFM). The resulting hollow PSS/PAH/CR/PDDA capsules displayed a sensitive response to visible light. Optical changes of the hollow capsules prior to and after the photoreaction were investigated in detail by means of UV-visible spectroscopy, CLSM, and SFM. It was found that the photochemical reaction of the assembled hollow capsules depends strongly on the matrix. Qualitative results on the permeability of the hollow capsule walls with CR as one component indicate that the permeability of the walls can be easily photo-controlled at varying irradiation time intervals without addition of external chemicals.     

Interactions of hemoglobin with lecithin liposomes

In this paper, the interaction of hemoglobin (Hb) with lecithin liposomes is studied by UV-vis spectroscopy, fluorescent spectroscopy, and transmission electron microscopy. The adsorption of Hb on liposomes is likely to be related to the hydrophobic interaction between Hb and liposomes, which brings about the increase of the microenvironmental polarity (I ₁/I ₃) and the decrease of the fluorescence polarization (P) of lecithin liposomes. These results are considered to be that the adsorption of Hb on liposomes makes the spaces between the lecithin molecules increase, and a temporary gap is consequently formed in the liposomal bilayer membranes. The leakage of aqueous-space marker from the liposomes is increased with the addition of Hb.     

Bioinspired manganese complexes catalyzed epoxidation for the synthesis of the epoxyketone fragment of carfilzomib

We report herein an efficient catalytic epoxidation reaction for the synthesis of epoxyketone (tert-butyl ((S)-4-methyl-1-((R)-2-methyloxiran-2-yl)-1-oxopentan-2-yl)carbamate), which is an important synthetic intermediate of carfilzomib.     

Study on the interaction between nucleic acids and cationic surfactants

The interactions of nucleic acids and cationic surfactants (cetylpyridine bromide (CPB) and cetyltrimethylammonium bromide (CTMAB)) in aqueous solution have been studied using the techniques of resonance light scattering (RLS) spectroscopy, the absorption spectroscopy, zeta potential assay and NMR assignment measurement. It is considered that CPB or CTMAB can assemble on the surface of nucleic acid via electrostatic and hydrophobic forces, which results in the formation of large associate of nucleic acid-cationic surfactant and RLS enhancement of nucleic acid. Besides these forces, the pi-pi stacking force between CPB and nucleic acid also exists in the associate. In comparison with CTMAB, CPB has larger enhancement on RLS of nucleic acid, which is attributed to that the enhancement of the former is only due to the absorption of the bases of nucleic acid, while the enhancement of the latter is own to the synergetic resonance caused by the absorption of both bases of nucleic acid and the pyridyl in CPB. These results have important implication for understanding the influence of surfactants on nucleic acid functionality in life science.