83 K光系统Ⅱ核心复合物不同激发的荧光光谱学

在83 K低温下,利用稳态荧光光谱技术对光系统Ⅱ（PSⅡ）核心复合物中激发能的传递进行了研究,激励波长分别选择为436 nm,480 nm,495 nm和507 nm,得到4种波长激发下的稳态荧光光谱.经过比较发现其最大峰值所在的位置没有因激发波长的不同而发生改变,都在696 nm处,在不同激发波长下经过高斯解析获得不同的谱带.根据发射光谱与吸收光谱的对应性,反映了不同的光谱特性,说明在不同波长光的激发下,核心复合物中能量传递的途径不同.同时,可以分析出在核心复合物中,至少有Chl a670.4670,Chl a684.7,685.1683,Chl a689.0687,Chl a690.9,693.4,695.2,698.06904种Chl a组分参与了能量的传递.     

Analysis of protective action of ischemic preconditioning from fluorescence spectra of blood serum and probes added to it

The protective effect of ischemic preconditioning on brain tissue during total ischemia is shown by using spectral-luminescence methods for estimating oxidative damage to blood components after ischemia. Fluorescence of blood serum and molecular probes added to it is investigated after producing brain ischemia with preconditioning. Lipid free-radical peroxide damage of low-density lipoproteins is found to decrease after producing ischemia with preconditioning rather than ischemia without preconditioning. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 378–381, May–June, 2007.     

The laser-induced fluorescence spectroscopy of CoF in the ultra violet region

The laser-induced fluorescence (LIF) spectrum of jet-cooled CoF has been obtained in the wavelength region of 260-290 nm for the first time. Seventeen vibronic bands were observed and assigned to three types of transition from the ground state to upper states Ω′ = 3, 4, 5 by rotational analysis. A new vibrational transition with the 0-0 band at 34697.22 cm⁻¹ has been assigned as the [34.7]³Γ₅-X³Φ₄ transition and effective equilibrium molecular constants for the upper state have been determined. In addition, lifetime measurements have been carried out for most of the bands under collision-free conditions. On the basis of the spectroscopic data and lifetime measurements, the electronic structures of these possible high-lying electronic states are discussed.     

Hysteresis of ruby fluorescent line by pressure and annealing effect

Abstract

Accuracy of hydrostatic pressure measurement in a diamond-anvil cell (DAC) depends on the reproducibility of ruby RI fluorescent measurement. The larger scatter in R, fluorescent wavelength shift than the reproducibility of spectroscopic measurement was observed among appropriately mirror-finished ruby plates before setting up in DAC. The characteristics of the scatter changed after loading DAC up to pressure over hydrostatic limit. They vanished by annealing the ruby plates. These phenomena are presumably due to the appearance and disappearance of the residual stress in the ruby crystal. Such hysteresis of ruby fluorescent wavelength shift by pressure and its annealing effect are discussed.     

Custom‐Fit Ruthenium(II) Metallopeptides: A New Twist to DNA Binding With Coordination Compounds

A new bipyridine building block has been used for the solid‐phase synthesis of dinuclear DNA‐binding ruthenium(II) metallopeptides. Detailed spectroscopic studies suggest that these compounds bind to the DNA by insertion into the DNA minor groove. Moreover, the potential of the solid‐phase peptide synthesis approach is demonstrated by the straightforward synthesis of an octaarginine derivative that shows effective cellular internalization and cytotoxicity linked with strong DNA interaction, as evidenced by steady‐state fluorescence spectroscopy and AFM studies.     

Quantification of ATRP initiator density on polymer latex particles by fluorescence labeling technique using copper‐catalyzed azide‐alkyne cycloaddition

We developed a novel fluorescence labeling technique for quantification of surface densities of atom transfer radical polymerization (ATRP) initiators on polymer particles. The cationic P(St‐CPEM‐C₄DMAEMA) and anionic P(St‐CPEM) polymer latex particles carrying ATRP‐initiating chlorine groups were prepared by emulsifier‐free emulsion polymerization of styrene (St), 2‐(2‐chloropropionyloxy)ethyl methacrylate (CPEM), and N‐n‐butyl‐N,N‐dimethyl‐N‐(2‐methacryloyloxy)ethylammonium bromide (C₄DMAEMA). ATRP initiators on the surface of polymer particles were converted into azide groups by sodium azide, followed by fluorescent labeling with 5‐(N,N‐dimethylamino)‐N′‐(prop‐2‐yn‐1‐yl)naphthalene‐1‐sulfonamide (Dansyl‐alkyne) by copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The reaction time required for both azidation of ATRP‐initiating groups and successive fluorescence labeling of azide groups with Dansyl‐alkyne by CuAAC were investigated in detail by FTIR and fluorescence spectral measurement, respectively. The ATRP initiator densities on the cationic P(St‐CPEM‐C₄DMAEMA) and anionic P(St‐CPEM) particle surfaces were estimated to be 0.21 and 0.15 molecules nm^?2, respectively, which gave close agreement with values previously determined by a conductometric titration method. The fluorescence labeling through click chemistry proposed herein is a versatile technique to quantify the surface ATRP initiator density both on anionic and cationic polymer particles. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4042–4051     

Conjugated polyelectrolytes and neutral polymers with poly(2,7‐carbazole) backbone: Synthesis,characterization, and photovoltaic application

Poly(2,7‐carbazole) neutral polymers (PC‐N, PC‐NOH, and PC‐P) and polyelectrolytes (PC‐NBr and PC‐SO₃Na) with hydrophilic pendant groups of ammonium, phosphonate, and sulfonate were synthesized as interlayers for cathode modifications in bulk‐heterojunction photovoltaic cells (BHJ PVCs). The absorptions of the polymers were determined by the poly(2,7‐carbazole) backbone, showing absorption peaks at ～390 nm for their solutions and films. Because of large intermolecular interactions, excimer emissions with wavelengths higher than 500 nm were found in the photoluminescence spectra of the films of the polymers, which weakened the light emissions of the polymers. PC‐N, PC‐NBr, PC‐NOH, and PC‐P possessed comparable HOMO levels of ?5.23 eV and LUMO levels of ?2.4 eV, but HOMO and LUMO levels of PC‐SO₃Na were up‐lying to ?4.91 and ?2.12 eV, respectively. PC‐N, PC‐NBr, PC‐NOH, and PC‐P were selected to construct thin interlayers in BHJ PVCs with PFO‐DBT35:PCBM = 1:4 as the active layer. Compared with traditional Al cathode, bilayer cathodes with the interlayers showed improvements of open‐circuit voltages and short‐circuit currents of the PVCs. PC‐NOH was the best for the photovoltaic performances and over 20% increase of power conversion efficiency (PCE) was achieved. The bilayer cathodes would have great potential to further elevate PCE of BHJ PVCs with other active layer materials. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of main‐chain poly(carbazole)s via CuAAC

The synthesis and characterization of a novel family of main‐chain carbazole‐containing polymers using copper‐catalyzed azide‐alkyne cycloaddition chemistry is reported. The reactions were performed under mild conditions using readily available copper catalysts and ligands, which afforded polymeric products with M_ws up to 18 kDa. Using a range of techniques, the polymers were found to exhibit a glass transition temperature (T_g) of 85 °C, high thermal stability (T_d = 274 °C), and high photoluminescent quantum efficiency (?_f = 0.29; λ_em = 448 nm), which underscore their potential for use in organic light‐emitting diodes or other emissive devices, particularly where efficient blue emission is of value. The approach described offers practical advantages over other synthetic methods used to prepare main‐chain carbazole‐containing polymers, especially with regard to the lack of need for rigorously inert conditions and the absence of byproducts generated during the polymerization reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Separation of single‐walled carbon nanotubes with aromatic group functionalized polymethacrylates and building blocks contribution to the enrichment

We previously showed that in N,N‐dimethylformamide (DMF), poly(9‐anthracenylmethyl methacrylate) (PAMMA) and poly(2‐naphthylmethacrylate) selectively disperse semiconducting and metallic single‐walled carbon nanotubes (SWNTs), respectively. We have also proposed a new noncovalent polymer interaction based on photon induced dipole–dipole interaction to account for the metallicity‐based selectivity. In this article, we investigate two other polymethacrylates, that is, poly(benzyl methacrylate) (PBMA) and poly(methylmethacrylate)‐co‐(9‐anthracenylmethyl acrylate) (PMMA‐c‐PAMA) in the light of our previously proposed photon‐induced dipole–dipole interaction. We find that PBMA and PMM‐c‐PAMMA in DMF show no metallicity selectivity. The different selective behavior of the four polymers in DMF manifests the decisive influence of the side aromatic group in determining their metallicity selectivity. The nonpreferential energy transfer from PMMA‐c‐PAMA to SWNTs and the nonoverlap of PBMA fluorescence (in the ultraviolet range) with nanotube absorption account for their nonselectivity of specific nanotube species. Further, the parallel relationship between the diameters of extracted tube species and the affinity between polymers and solvents suggests the leading role of the polymeric conformation on the diameter selectivity. A sufficient (i.e., 2 weeks) standing time of the SWNTs solution after sonication, during which the polymers presumably optimize their conformation to the SWNTs, was found to be essential to the enrichment. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011