富勒烯(C60／C70)与N，N，N’，N’-四-(对甲苯基)-4，4’-二胺-1，1’-二苯硒醚(TPDASe)间光诱导电子转移过程的激光光解研究

富勒烯(C60／C70)与N，N，N’，N’-四-(对甲苯基)-4，4’-二胺-1，1’-二 苯硒醚(TPDASe)间在激光光诱导条件下，发生了分子间的电子转移过程．在可见- 近红外区(600-1200nm)，观测到了TPDASe阳离子自由基、富勒烯(C60／C70)激发三 线态和阴离子自由基，在苯腈溶液中，观测瞬态谱测定了电子从TPDASe转移到富勒 烯(C60／C70)激发三线态的量子转化产率(Φet^T)和电子转移常数(Ket)．     

On-line concentration of s-triazine herbicides in micellar electrokinetic chromatography using a cationic surfactant

A new method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was investigated using high-performance ion-exclusion/cation-exchange chromatography with conductimetric detection on a separation column packed with a polymethacrylate-based weakly acidic cation-exchange resin in the hydrogen-form and an eluent comprising 1.5 mM sulfosalicylic acid–6 mM 18-crown-6 at pH 2.6, operated at 1.5 ml/min. Effective separation and highly sensitive conductimetric detection for the anions and the cations was achieved in about 14 min. Since the ionic balance (equivalents of anions/equivalents of cations) of acid rain waters of different pH (4.40–4.67) ranged from 0.97 to 0.94, evaluation of the water quality of acid rain was possible. This method was successfully applied to the simultaneous determination of the anions and the cations in acid rain transported from mainland China and North Korea to central Japan monitored by a meteorological satellite data analyzer.     

Detection of traces of oxidized and reduced sulfur compounds in small samples by combination of different high-performance liquid chromatography methods

Depending on the sulfur species, picomoles of different inorganic sulfur compounds can be detected and separated by HPLC in one arrangement in a sample volume less than 50 μl. The combination of fluorescence labelling of reduced inorganic sulfur compounds such as sulfide (S²⁻), sulfite(SO₃²⁻ and thiosulfate (S₂O₃²⁻) with monobromobimane followed by an extraction of elemental sulfur (S°) by chloroform treatment enables the detection of all mentioned sulfur compounds as well as sulfate (remaining aqueous phase) in the same sample. While the derivatized sulfur compounds could be detected by their fluorescence emission at 480 nm, elemental sulfur is identified by its UV absorption at 263 nm. Sulfate in the remaining aqueous phase is detected by HPLC with indirect UV detection at 254 nm. Detection ranges for the different sulfur compounds examined are as follows: sulfide (5 μM to 1.5 mM), sulfite (5 μM to 1.0 mM), thiosulfate (1 μM to 1.5 mM), elemental sulfur (2 μM to 32 mM) and sulfate (5 μM to >1 mM).     

Electrochemically formed fullerene-based polymeric films

The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C₆₀/Pt and C₆₀/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C₆₀/M and C₇₀/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C₅₉M]⁺ and [C₆₉M]⁺.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday.     

微波辅助萃取-HG-AFS测定土壤中无机砷

采用微波辅助萃取分析物,联合原子荧光光谱技术,建立了微波辅助萃取-HG-AFS测定土壤中无机砷的分析方法。用正交试验设计结合单因素试验优化了样品粒度、萃取温度、萃取时间、固液比等微波萃取条件,研究了共存离子对无机砷测定的干扰情况。方法的线性范围为1.0~160.0μg/L,无机砷的检出限为0.20μg/L,相对标准偏差为0.3%,样品回收率为93.0%~98.5%。用本法分析3个不同产地有代表性土壤中无机砷量。     

Toxic Effect of Fullerene and Its Derivatives upon the Transmembrane β2-Adrenergic Receptors

Numerous experiments have revealed that fullerene (C₆₀) and its derivatives can bind to proteins and affect their biological functions. In this study, we explored the interaction between fullerine and the β₂-adrenergic receptor (β₂AR). The MD simulation results show that fullerene binds with the extracellular loop 2 (ECL2) and intracellular loop 2 (ICL2) of β₂AR through hydrophobic interactions and π–π stacking interactions. In the C₆₀_in1 trajectory, due to the π–π stacking interactions of fullerene molecules with PHE and PRO residues on ICL2, ICL2 completely flipped towards the fullerene direction and the fullerene moved slowly into the lipid membrane. When five fullerene molecules were placed on the extracellular side, they preferred to stack into a stable fullerene cluster (a deformed tetrahedral aggregate), and had almost no effect on the structure of β₂AR. The hydroxyl groups of fullerene derivatives (C₆₀(OH)_X, X represents the number of hydroxyl groups, X = 4, 8) can form strong hydrogen bonds with the ECL2, helix6, and helix7 of β₂AR. The hydroxyl groups firmly grasp the β₂AR receptor like several claws, blocking the binding entry of ligands. The simulation results show that fullerene and fullerene derivatives may have a significant effect on the local structure of β₂AR, especially the distortion of helix4, but bring about no great changes within the overall structure. It was found that C₆₀ did not compete with ligands for binding sites, but blocked the ligands’ entry into the pocket channel. All the above observations suggest that fullerene and its derivatives exhibit certain cytotoxicity.     

显微红外光谱法研究聚乙烯复合材料光氧化的深度分布

采用显微红外光谱法结合表面形貌分析研究了分别填充碳酸钙、绢英粉、云母、高岭土和硅藻土的高密度聚乙烯(HDPE)的自然光氧化随深度的分布。研究结果表明无机填料对HDPE光氧化的深度分布有很大的影响。填充碳酸钙的HDPE从表面到内部都没有明显氧化发生。而填充绢英粉、云母、高岭土和硅藻土的HDPE从表面到内部羰基指数逐渐减小,氧化深度都在150 μm以上。HDPE复合材料沿深度方向的氧化情况与其断面裂纹的产生情况吻合。结合无机填料的紫外吸收特性讨论了它们对HDPE光氧化的影响机理。     

Synthesis of Cationic Dumbbell-shaped Fullerene Nanostructures as Potential Photodynamic Sensitizers

A design of novel hydrophilic tetracationic dumbbell-shaped [60]fullerene nanostructures was made by balancing the hydrophilicity and hydrophobicity characteristics of the fullerene adduct for their potential application as photodynamic sensitizers in the PDT treatment. A sequential protection-deprotection reaction pathway was applied for the functional differentiation between primary and secondary amine moieties of pentaethylene hexamine. Synthesis of the target molecule involves two key steps of unsymmetrical esterification and amidation of malonic acid and subsequent fullerenation. The synthetic strategy was accomplished using mild reaction conditions in the intermediate molecule preparation and led a moderate overall product yield.     

Open‐cage fullerenes as tailor‐made container for a single water molecule

Water is the most important liquid on earth. Clusters of water have been investigated extensively in an effort to understand the bulk property of water. But the behavior of single water molecule without H‐bond has been rarely studied. Open‐cage [60]fullerenes have been shown to trap a single water molecule selectively over molecules with comparable size and act as the smallest “water bottle”. Copyright © 2013 John Wiley & Sons, Ltd.     

Fullerene compounds with general formulae C60Ox (x = 1–3): Isomerism,stability and polarizability

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