Oligodeoxyfluorosides: Strong Sequence Dependence of Fluorescence Emission

We describe the properties of a series of oligomeric polyfluorophores assembled on the DNA backbone. The 11 oligomers (oligodeoxyfluorosides, ODFs), 4-7 monomers in length, were composed of only two fluorescent monomers and a spacer in varied sequences, and were designed to test how fluorescent nucleobases can interact electronically to yield complexity in fluorescence emission. The monomer fluorophores were deoxyribosides of pyrene and perylene, which emit light in violet and blue wavelengths, respectively. The experiments show that simple variation in sequence and spacing can dramatically change fluorescence, yielding emission maxima ranging from 380 to 557 nm and visible colors from violet to orange-red. Fluorescence lifetime data, excitation spectra, and absorption data point to a number of multi-fluorophore electronic interactions, including pyrene-pyrene and perylene-perylene excimers, pyrene-perylene exciplexes, as well as monomer dye emissions, contributing to the final spectral outcomes. Thus, two simple fluorophores can be readily combined to give emissions over much of the visible spectrum, all requiring only a single excitation. The results demonstrate that fluorescent nucleobases in oligomeric form can act cooperatively as electronic units, and that fluorophore sequence in such oligomers is as important as fluorophore composition in determining fluorescence properties.     

具有全氟丁基磺酰亚胺基侧链的聚磷腈的合成

本文合成了一种新的具有全氟丁基磺酰亚胺基侧链的聚磷腈高分子。并用¹H NMR、 ¹⁹F NMR、 IR光谱、凝胶渗透色谱以及热重分析等方法, 对其结构和性质进行了表征。     

Does core size matter in the kinetics of ligand exchanges of monolayer-protected Au clusters?

This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X.     

One-step preparation of highly concentrated well-stable gold colloids by direct mix of polyelectrolyte and HAuCl4 aqueous solutions at room temperature

Highly concentrated, well-stable gold colloids can be prepared directly from an amine-bearing polyelectrolyte-HAuCl4 aqueous solution at room temperature. It is found that increasing molar ratio of polyelectrolyte to gold leads to increasing particle size. UV-vis spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) were used to characterize the products thus formed.     

A solvothermal synthesis and the structure of K4Ag2Sn3S9 x 2KOH

A novel layered K(4)Ag(2)Sn(3)S(9) x 2KOH was synthesized solvothermally. A mixture of ethanol and HSCH(2)CH(SH)CH(2)OH was used for the synthesis. The HSCH(2)CH(SH)CH(2)OH plays an important role and appears to serve as a mineralizer for the solvothermal reaction. A layer comprises Sn(3)S(9)(6)(-) clusters linked by Ag(+) ions and possesses two types of 1D channels in which potassium ions are located. The compound crystallizes in the monoclinic P2(1)/m space group [a = 7.8071(2) A, b = 27.3508(1) A, c = 10.5008(2) A, alpha = 90 degrees, beta = 103.874(1) degrees, gamma = 90 degrees, Z = 4]. Its crystal structure, composition analysis, and IR are presented.     

Direct observation of eta 2-imine formation through beta-H abstraction between amide ligands. Neutron and X-ray diffraction structure of a dihydride imine ditantalum complex

Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction.     

Study of occupational health impact of atmospheric pollution on exposed workers at an iron and steel complex by using neutron activation analysis of scalp hair

The occupational health impact of atmospheric pollution on exposed workers at one iron and steel complex was studied by instrumental neutron activation analysis of workers' hair samples and medical examination. The experimental results indicate that there is a positive correlation between the high inhalation amounts of iron and other trace elements by the exposed workers and the symptom of their high blood pressure and hypoglycemia, which implies that the atmospheric environment polluted by iron and steel industry has an adverse health impact on the exposed workers. The measures to relieve and abate the occupational diseases caused by air-borne particulate matter should be taken     

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalated α-zirconium phosphate micro particles

Methylene blue-intercalated alpha-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V ( vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1x10(-6)-4x10(-3) mol x L(-1) and 1.5x10(-7) mol x L(-1), respectively.     

离子缔合富集明极溶出伏安法测定痕量碘——Ⅰ.以丁基罗丹明B为离子缔合剂

本文提出在0.1mol/LH_2SO_4,7.5×10~(-4)mol/LBr~-和6×10~(-5)mol/L丁基罗丹明B(R~+)的底液中,在+1.0V下,I~-离子于玻璃电极上被氧化生成I_2BrR离子缔合物,藉以阴极溶出伏安法测定碘、I~-离子浓度在1～50ppb范围内与峰电流呈线性关系。用于食盐中痕碘的测定。     

Photoassociative spectroscopy of pure long-range molecules

We have experimentally studied the “pure long-range” state, 0 _g ^? , of³⁹K₂ for the first time by high resolution photoassociative spectroscopy of ultracold potassium atoms. Well-resolved vibrational levels have yielded molecular constants for this state. Analytical expressions for the potential energy curves of the two pure long-range states, 0 _g ^? and 1 _u , are obtained. All the available theoretical and experimental molecular constants of the three special long-range potentials with extrema for all the alkali metals are summarized.