Starburst substituted hexaazatriphenylene compounds: synthesis, photophysical and electrochemical properties

Starburst-substituted hexaazatriphenylene Compounds have been designed and synthesized by introducing various peripheral aryl substituents to the central heterocyclic core. The effects of various substituent groups on the photophysical and electrochemical properties of the substituted hexaazatriphenylene have been investigated. Significant red-shifts of the absorption peak (from 413 nm to 530 nm) and emission peak (from 432 nm to 700 nm) were observed when the electron-donating ability of the aryl substituents was increased, corresponding to a decrease in the band gap from 2.90 eV to 2.05 eV. Introducing bulky substituents with weak electron-donating ability enhances the fluorescence quantum yield from 23% to 87%. In contrast, incorporating aryl substituents with strong electron-donating ability decreases the fluorescence quantum yield.

Interactions of the human telomeric DNA with terbium-amino acid complexes

The human telomeric DNA can form four-stranded structures: the G-rich strand adopts a G-quadruplex conformation stabilized by G-quartets and the C-rich strand may fold into an I-motif based on intercalated C (.) C+ base pairs. There is intense interests in the design and synthesis of compounds which can target telomeric DNA and inhibit the telomerase activity. Here we report the thermodynamic studies of the two newly synthesized terbium-amino acid complexes bound to the human telomeric G-quadruplex and I-motif DNA which were studied by means of UV-Visible, DNA meltings, fluorescence and circular dichroism. These two complexes can bind to the human telomeric DNA and have shown different features on DNA stability, binding stoichiometry, and sequence-dependent fluorescence enhancement. To our knowledge, this is the first report to show terbium-amino acid complexes can interact with the human telomeric DNA.

Characterization of the structural and functional changes of hemoglobin in dimethyl sulfoxide by spectroscopic techniques

Circular dichroism (CD), fourier transform infrared (FTIR), and fluorescence spectroscopy were used to explore the effect of dimethyl sulfoxide (DMSO) on the structure and function of hemoglobin (Hb). The native tertiary structure was disrupted completely when the concentration of DMSO reached 50% (v/v), which was determined by loss of the characteristic Soret CD spectrum. Loss of the native tertiary structure could be mainly caused by breaking the hydrogen bonds, between the heme propionate groups and nearby surface amino acid residues, and by disorganizing the hydrophobic interior of this protein. Upon exposure of Hb to 52% DMSO for ca. 12 h in a D2O medium no significant change in 1652 cm(-1) band of the FTIR spectrum was produced, which demonstrated that alpha-helical structure predominated. When the concentration of DMSO increased to 57%: (1) the band at 1652 cm(-1) disappeared with the appearance of two new bands located at 1661 and 1648 cm(-1); (2) another new band at 1623 cm(-1) was attributed to the formation of intermolecular beta-sheet or aggregation, which was the direct consequence of breaking of the polypeptide chain by the competition of S=O groups in DMSO with C=O groups in amide bonds. Further increasing the DMSO concentration to 80%, the intensity at 1623 cm(-1) increased, and the bands at 1684, 1661 and 1648 cm(-1) shifted to 1688, 1664 and 1644 cm(-1), respectively. These changes showed that the native secondary structure of Hb was last and led to further aggregation and increase of the content of 'free' amide C=O groups. In pure DMSO solvent, the major band at 1664 cm(-1) indicated that almost all of both the intermolecular beta-sheet and any residual secondary structure were completely disrupted. The red shift of the fluorescence emission maxima showed that the tryptophan residues were exposed to a greater hydrophilic environment as the DMSO content increased. GO-binding experiment suggested that the biological function of Hb was disrupted seriously even if the content of DMSO was 20%. (C) 1998 Elsevier Science B.V. All rights reserved.

Bi-Sr-Ca-Cu-O体系中可能存在一个新的高T_c超导相

最近,Pb能加强BiSrCaCuO超导体中高T_c相(即2223相,其c(?)37,T_c(?)110K)的出现和掺入sb形成BiPbSbSrCaCuO的T_c可以达到132 K已见报道,我们希望通过其它元素的掺杂取代也出现类似的结果。我们做了大量掺Sb、Ba、In的实验,通过改变

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

Sulfide: quinone oxidoreductase (SQR) is a flavoprotein with homologues in all domains of life except plants. It plays a physiological role both in sulfide detoxification and in energy transduction. We isolated the protein from native membranes of the hyperthermophilic bacterium Aquifex aeolicus, and we determined its X-ray structure in the "as-purified,'' substrate-bound, and inhibitor-bound forms at resolutions of 2.3, 2.0, and 2.9 angstrom, respectively. The structure is composed of 2 Rossmann domains and 1 attachment domain, with an overall monomeric architecture typical of disulfide oxidoreductase flavoproteins. A. aeolicus SQR is a surprisingly trimeric, periplasmic integral monotopic membrane protein that inserts about 12 angstrom into the lipidic bilayer through an amphipathic helix-turn-helix tripodal motif. The quinone is located in a channel that extends from the si side of the FAD to the membrane. The quinone ring is sandwiched between the conserved amino acids Phe-385 and Ile-346, and it is possibly protonated upon reduction via Glu-318 and/or neighboring water molecules. Sulfide polymerization occurs on the re side of FAD, where the invariant Cys-156 and Cys-347 appear to be covalently bound to polysulfur fragments. The structure suggests that FAD is covalently linked to the polypeptide in an unusual way, via a disulfide bridge between the 8-methyl group and Cys-124. The applicability of this disulfide bridge for transferring electrons from sulfide to FAD, 2 mechanisms for sulfide polymerization and channeling of the substrate, S2-, and of the product, S-n, in and out of the active site are discussed.

Millstone Hill电离层F层等效风场的气候学研究

Neutral winds and electric fields in the ionospheric F layer play important roles in the variations of the ionosphere, and also affect the thermospheric circulation via the close coupling between the ionosphere and the thermosphere. By now, the neutral winds and electric drifts are generally observed with ground-based Fabry-Perot interferometers (FPI) and incoherent scatter radars (ISR), rockets, and satellite-borne instrument. Based on the servo theory, the ionospheric equivalent winds, which include the information of both the neutral winds and electric fields, can be derived from these characteristic parameters observed by ionosondes. This indirect derivation has potential values in climatological researches and space weather forecast. With the data set of the incoherent scatter radar observations at Millstone Hill, USA, from 1976 to 2006, we statistically analyzed the climatological variations of the vertical component of the equivalent winds (VEWs) over Millstone Hill, which are derived from the ionospheric key parameters (the peak electron number density and peak height of the F2 layer, NmF2 and hmF2) on the basis of the servo theory, Liu's method, and measurements from the ion line-of-sight velocity as well. The main results of this analysis are summarized as follows: (1) The values of VEWs over Millstone Hill during nighttime are stronger than in the daytime, and the upward drift dominates most of the day. In 1993, Hagan found that the component of the neutral winds in the magnetic meridion in daytime is weaker than during nighttime under both solar maximum and minimum conditions; he also found that the equatorward winds dominate most of the day. Both results suggest that the thermosphere in Millstone Hill is modulated by the aurorally driven high-latitude circulation cell; that is, during geomagnetic quiet periods, the average auroral activity is strong enough to drive thermospheric circulation equatorward for most of the day at Millstone Hill. Moreover, since ion drag is the strongest during daytime when F region densities are enhanced by photoionization, the wind speeds are smaller during the daytime than in the nighttime. (2) There is equinoctial symmetry in VEWs at Millstone Hill. The amplitudes and phases of VEWs in spring are quite similar to those in autumn. In contrast, the nighttime upward drift in winter is weaker than in summer and the difference becomes more significant with increasing solar activity. This solstice asymmetry indicates that, the aurorally driven circulation in the northern hemisphere at Millstone Hill latitude is weaker in winter due to arctic darkness, because the subsolar point is in the southern hemisphere. (3) The comparison of the VEWs derived from three methods, i.e., the servo theory, Liu's method, and the ISR ion line-of-sight velocity measurements, indicates that the amplitudes and main phase tendencies of these VEWs accord well with each other during nighttime hours. However, the case in the daytime is relatively worse. This daytime discrepancy can be explained in terms of the effects of photochemical processes and the choices of the servo constants. A larger servo constant gives a stronger plasma drift in daytime. Therefore, this study tells how important to choose a suitable constant for deriving VEWs at Millstone Hill.