碱蓝6B共振光散射法检测DNA

研究了碱蓝 6B与脱氧核糖核酸在酸性条件下共振光散射特征 ,考察了影响因素和最佳反应条件 ,建立了一种测定纳克级DNA的方法。在四硼酸钠 盐酸 (pH =2 90 )缓冲溶液中 ,线性范围为 10～ 10 0 4 μg·L- 1 ,相关系数为 0 9913,检出限为 4 2 μg·L- 1 ,用于合成样品的测定结果令人满意。     

Über die Magnetischen Eigenschaften der Cobaltate Na6CoS4, Na6CoSe4 und K6CoS4

Magnetic Properties of the Cobaltates Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ The alkali metal cobalt chalcogenides Na₆CoS₄, Na₆CoSe₄, and K₆CoS₄ crystallize in the space group P6₃mc with Z = 4. The structure is characterized by isolated [CoX₄]-tetrahedra. The magnetic susceptibilities show Curie-Weiss behaviour. The deviations at low temperatures are caused by antiferromagnetic interactions. The magnetic moments are discussed with regard to ligand-field parameters.     

A Generalized Unpaired Electron Spin Density Equation and Organic Hyperconjugation Mechanism

A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules.     

Effect of various adsorbates in dephasing and population decay of the Cu(1 0 0) image potential states

A theoretical study of the electron dynamics in image potential states on Cu(1 0 0) surfaces with different types of adsorbates is presented. Scattering of the image state electron by an adsorbate induces inter-band and intra-band transitions leading respectively to the population decay and to the dephasing of the image state. We compare results obtained with low coverage (typically 1 adsorbate atom per 1000 surface atoms) Cs, Ar, and a model electronegative adsorbates. As follows from our results, Cs adsorbates lead to both appreciable dephasing and decay, while electronegative adsorbates mostly affect the dephasing rate. The effect of low coverage Ar adsorbates is small, consistent with their neutrality.     

A New Family of Binary Layered Compounds of Platinum with Alkali Metals (A = K,Rb, Cs)

By reacting platinum with alkali metals (A = K, Rb, Cs) a new family of binary alkali metal platinides has been synthesized and characterized by chemical analysis, X‐ray powder diffraction, thermal analysis (DTA and DSC), and magnetic measurements. All three compounds exhibit similar XRD‐patterns with strong reflections that can be indexed on the basis of a rhombohedral crystal system (K_xPt: a = 2.6462(1), c = 17.123(1); Rb_xPt: a = 2.6415(1) Å, c = 17.871(1) Å; Cs_xPt: a = 2.6505(1) Å, c = 18.536(1) Å; x < ½. The a lattice constant is independent on the alkali metal used and of value close to the Pt–Pt distance in NaPt₂ (2.645Å). The c parameter increases monotonically with the growing atomic radius of the alkali metal. The average structure of the alloys consists of cubic close packed layers of platinum atoms with layers of disordered alkali metals in between. For all compounds besides the strong reflections small satellites are observed which cannot be indexed together with the rhombohedral peaks in any rational 3‐dimensional lattice. However, these satellites can be indexed as incommensurate modulations within the ab plane (found propagation vectors k = (0.1011, 0.2506, 0) for Cs_xPt, and k = (0.0168, 0.2785, 0) for Rb_xPt).     

Multifunctional Calix[4]arenes Containing Pendant Amide and Phosphoryl Groups: Their Use as Extracting Agents and Carriers for Alkali Cations

The complexing, extracting and mobile carrier properties of the tetra(phosphine oxide)-calix[4]arene 1 and the hybrid diamide-di(phosphine oxide)-calix[4]arene 2 were studied. Both ligands give 1 : 1 complexes with alkali cations in THF as shown by the picrate method. 1H NMR experiments were run to follow encapsulation of sodium and potassium cations. The corresponding spectra indicate C2-symmetrical structure. The observed extraction orders of the alkali picrates were as follows K+>Rb+>Li+>Cs+>Na+ for 1 and Li+>Na+>K+>Rb++ for 2. Transport kinetics was analysed by means of a model which assumes pure diffusion and which allows the evaluation of mass transfer coefficients in all systems. These coefficients and their influences on the transport rate are discussed in terms of size of the transporting species in the liquid membrane.     

Solubility and Ionic Processes in the Cu X 2? MX ?H2O ( X ?=Cl?, Br?; M +=Li+, Na+, K+, NH4+, Cs+) Systems

Summary.  Solubility isotherms in the CuBr₂−MBr−H₂O (M ⁺ = Li⁺, Na⁺, Cs⁺) systems at 298.15 K were measured. The results together with other available literature data for copper chloride and bromide systems were treated by hydration analysis, and comparative discussion of ionic processes taking place in the respective saturated solutions was performed. Corresponding author. E-mail: jitka@prfdec.natur.cuni.cz Received August 6, 2002; accepted (revised) November 29, 2002 Published online April 3, 2003     

Zig‐Zag Diphosphene Oligomers Linked by Silver(I) Cation

The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = ^tBu₃C₆H₂) was investigated in detail. The reaction of 1 with Ag[Al(OR_F)₄] (OR_F = OC(CF₃)₃) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH₂Cl₂ molecules.     

Golden crowns: cation binding by macrocyclic gold(I) crown ether derivatives

The polyether bis(alkynes) α,ω-bis(O-propargyl)triethylene glycol and α,ω-bis(O-4-propargyloxyphenoxy)triethylene glycol reacted with [AuCl(SMe₂)] in the presence of base to form the corresponding oligomeric gold(I) acetylide complexes (AuCCCH₂O(CH₂CH₂O)₃CH₂CCAu)_n and (AuCCCH₂OC₆H₄O(CH₂CH₂O)₃C₆H₄OCH₂CCAu)_n. These digold(I) diacetylide complexes reacted with diphosphine ligands to give macrocyclic digold(I) complexes of the type [Au₂(μ-CC)(μ-PP)], where CC is the diacetylide and PP is a diphosphine ligand. These digold(I) complexes bind the cations Li⁺, Na⁺, K⁺ and Cs⁺, as studied by electrospray mass spectrometry.     

Einkristalluntersuchungen an Fluoroperowskiten MPdF3 (M = Rb,K) und PdF2

Single Crystal Investigations on Fluoroperovskites MPdF₃ (M = Rb, K) and PdF₂ Single crystal investigations on PdF₂ (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P4₂/mnm-D (No. 136) (x_F = 0.3058(8)). RbPdF₃ and KPdF₃ have been obtained. RbPdF₃ and KPdF₃ both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF₃) respectively a = 424.30(4) pm (KPdF₃).