Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides

Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)₂(dppz)]²⁺ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm⁻¹ for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied.

Efficient electron transfer requires the complex to be intercalated at a G-C base-pair. Identification of preferred intercalation sites is achieved by TRIR monitoring of the nucleobase vibrations before electron transfer.     

Development of a mild mercaptoethanol extraction method for determination of mercury species in biological samples by HPLC–ICP-MS

A mild, efficient and convenient extraction method of using 2-mercaptoethanol contained extractant solution combined with an incubator shaker for determination of mercury species in biological samples by HPLC–ICP-MS has been developed. The effects of the concentration of 2-mercaptoethanol, the composition of the extractant solution and the shaking time on the efficiency of mercury extraction were evaluated. The optimization experiments indicated that the quantitative extraction of mercury species from biological samples could be achieved by using 0.1% (v/v) HCl, 0.1% (v/v) 2-mercapoethanol and 0.15% (m/v) KCl extractant solution in an incubator shaker for shaking overnight (about 12 h) at room temperature. The established method was validated by analysis of various biological certified reference materials, including NRCC DOLT-3 (dogfish liver), IAEA 436 (tuna fish), IAEA MA-B-3/TM (garfish filet), IAEA MA-M-2/TM (mussel tissue), GBW 08193 (bovine liver) and GBW 08572 (prawn). The analytical results of the reference materials were in good agreement with the certified or reference values of both methyl and total mercury, indicating that no distinguishable transformation between mercury species had occurred during the extraction and determination procedures. The limit of detection (LOD) for methyl (CH₃Hg⁺) and inorganic mercury (Hg²⁺) by the method are both as 0.2 μg L⁻¹. The relative standard deviation (R.S.D.s) for CH₃Hg⁺ and Hg²⁺ are 3.0% and 5.8%, respectively. The advantages of the developed extraction method are that (1) it is easy to operate in HPLC–ICP-MS for mercury species determination since the extracted solution can be directly injected into the HPLC column without pH adjustment and (2) the memory effect of mercury in the ICP-MS measurement system can be reduced.     

Velocity map imaging of the photolysis of n-C4H9Br in UV region

Using velocity map ion imaging technique, the photodissociation of n-C₄H₉Br in the wavelength range 231–267 nm was studied. The results and our ab initio calculations indicated that the absorption of n-C₄H₉Br in the investigated region originated from the excitations to the lowest three repulsive states, as assigned as 1A″, 2A′ and 3A′ in C_s symmetry. Dissociations occurred on the PES surfaces of the three states, terminating in C₄H₉+Br (²P_3/2) or C₄H₉ + Br^* (²P_1/2) as two channels, and being impacted by an avoided crossing between the PES surfaces of the 2A′ and 3A′ states. The transition dipole to the 1A″ state was perpendicular to the symmetry plane, so perpendicular to the C–Br bond. The transitions to the 3A′ state was polarized parallel to the symmetry plane, and also parallel to the C–Br bond. While the transition dipole to the 2A′ state was in the symmetry plane, but formed an angle of about 53.1° with the C–Br bond. We have also determined the avoided crossing probabilities, which affected the relative fractions of the individual pathways, for the photolysis of n-C₄H₉Br near 234 nm and 267 nm.     

Structures and electrochemical characteristics of several kinds of alloys

The structures and the electrochemical characteristics of La_0.7−x Ce_xMg_0.3Ni_2.8Co_0.5 (x = 0.1–0.5) alloy, Ti_0.25−x Zr_xV_0.35Cr_0.1Ni_0.3 (x = 0.05–0.15) alloy and AB_3<x<5-type alloy, which are the representative examples of AB₃-type alloy, solid solution alloy and non-AB₅-type alloy, respectively, have been investigated, and the performances of MH-Ni battery in which AB_3<x<5 type alloy is used as the negative electrode material are examined at relatively low temperature.     

Ruthenium(II)-salen complexes-catalyzed olefination of aldehydes with ethyl diazoacetate

Several salen-ruthenium(II) complexes, which are derived from commercial ligands or simply ethylenediamine, can be successfully applied as catalysts for the olefination of a broad variety of aldehydes. Depending on the electron richness of the applied aldehydes, good to very good olefin yields and high E:Z selectivities are reached at 60 or 80 °C reaction temperature with ethyl diazo acetate being the reaction partner. The reaction rate depends on the electron donor capabilities of the aldehydes. Electron poor aldehydes undergo faster reactions than electron rich aldehydes, but both electron rich and bulky aldehydes can be transformed to corresponding olefins in very good yields and high E-selectivity.     

预处理条件对Zn/Al-CLM的丙烷芳构化性能的影响

在脉冲微反装置上考察了不同的预处理条件对Zn/Al-CLM催化剂的丙烷芳构化反应的影响。结果表明，丙烷在Zn/Al-CLM催化剂上具有一定的的反应活性和芳烃选择性，而且芳构化主要转化为苯；载体Al-CLM的焙烧温度、金属锌负载量、活化温度等对Zn/Al-CLM催化剂的丙烷芳构化性能具有重要影响。载体经500℃预焙烧制备的Zn/Al-CLM催化剂具有最好的柱结构保留度，从而表现出最佳的芳构化性能；随着锌含量的增加，Zn/Al-CLM催化剂的酸量增大，从而使丙烷转化率增大，而选择性则是锌含量质量分数为5．8％时具有极大值；400℃活化处理可使Zn与Al-CLM之间具有适中的相互作用，从而使得Zn/Al-CLM具有较高的芳烃收率。     

First alkyl radical additions to (eta(6)-arene)tricarbonylmanganese complexes

[reaction: see text] Reactions of alkylmercury chlorides with arene manganese tricarbonyl complexes in the presence of NaI led to the formation of the addition-reduction products. The mechanism was postulated to be the alkyl radical addition to ArMn(CO)3+ cation to form the corresponding 17 valence electron intermediate, which was then reduced by alkylmercury chloride via a singlet electron transfer process to afford the product and regenerate an alkyl radical.     

116例冠心病患者血清中钙镁钡铝锶含量的研究

测定１１６例冠心病患者血清中钙，镁，钡，铝和锶的含量并与正常值比较，常量元素钙，镁和微量元素锶降低，而微量元素钡和铝升高，它们之间的差异都有显著或高度显著性。Ｐ〈０．０５或Ｐ〈０．０１。     

水相中金属铜表面生成亚铜—邻菲罗啉配合物的反应

本文研究了零价铜在邻菲罗啉水溶液中的反应。当溶液敞露于空气并存在有机阴离子Ｘ－时，例如苯甲酸盐（Ｂｚ）、对甲基苯磺酸盐（Ｔｓ）等，铜的表面生成了致密的反应产物的薄层，经ＩＲ、ＵＶ／ＶＩＳ、ＭＳ和元素分析证明了该薄层为相当纯的亚铜的邻菲罗啉配位化合物，结构为［Ｃｕ（ｐｈｅｎ）２］＋Ｘ－。在乙醇／甲苯混合溶剂中得到了表面反应产物的晶体［Ｃｕ（ｐｈｅｎ）２］（ＣＨ３Ｃ４Ｈ６ＳＯ３）Ｃ２Ｈ５ＯＨ，并用Ｘ－ｒａｙ测得了结构。本工作表明溶液中的ＣｕⅡ离子抑制Ｃｕ０氧化成ＣｕⅠ而影响反应层的形成，同时又促进ＣｕⅠ氧化成ＣｕⅡ的过程     

溶胶—凝胶合成（Mg,Ca）O—SiO2：Eu^3＋,Bi^3＋发光体及其发光行为

以Ｍｇ（ＮＯ３）２，Ｃａ（ＮＯ３）２，Ｅｕ（ＮＯ３）３，Ｂｉ（ＮＯ３）３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度，首次合成０．７０１ｍｏｌＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏｌＳｉＯ２：０．０６ｍｏｌＥｕ＾３＋，０．００２ｍｏｌＢｉ＾３＋（加入Ｌｉ＾＋作为电荷补偿剂）发光体，得到了最佳合成条件，研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程，探讨了发光体在不同激光