A FLUORESCENCE STUDY OF THE BINDING OF HOECHST 33258 and DAPI TO HALOGENATED DNAs

We have studied the time-resolved and the steady-state fluorescence of the DNA groove binders 4',6-diamidino-2-phenylindole (DAPI) and Hoechst 33258 with the double stranded DNAs poly(dA-dU) and poly(dI-dC) and their halogenated analogs, poly(dA-I5dU) and poly(dI-Br5dC). These studies were prompted by earlier observations that steady-state fluorescence of Hoechst 33258 is quenched on binding to halogenated DNAs (presumably due to an intermolecular heavy atom effect involving the halogen atom in the major groove), and recent studies which clearly point to a binding-site in the minor groove of DNA. Measurements of the time resolved fluorescence decay demonstrate that the fluorescence of Hoechst 33258 is quenched on binding to the halogenated DNAs, in agreement with previous observations. However, quenching studies carried out using the free halogenated bases IdUrd and BrdCyd in solution yielded bimolecular rate constants more than one order of magnitude larger than those expected for an intermolecular heavy atom effect. Moreover, the quenching of the Hoechst 33258 fluorescence was accompanied by an accelerated photochemical destruction of Hoechst 33258. We therefore conclude that the fluorescence quenching observed with halogenated DNAs is probably due to a photochemical reaction involving Hoechst 33258, rather than direct contact of Hoechst 33258 with the halogen substituents in the major groove of the DNA. The fluorescence decay measurements however, do provide clear evidence for at least two different modes of binding. Taking into account the alternating sequences used in this study and the possibility of two different conformations for bound dye, at least four different modes of binding are plausible. Our present data do not allow us to distinguish between these alternatives. The time-resolved fluorescence decays and fluorescence quantum yields of DAPI are not affected by the presence of the heavy atom substituents in the DNA major groove. Based on this observation and earlier reports that DAPI binds in one of the DNA grooves, we conclude that the high affinity sites for DAPI on DNA are located in the minor groove.     

Molecular vibrational constants of some simple polyatomic molecules : Valence force constants and compliance constants of some halogenated methanes, silanes and germanes

The valence force constants and compliance constants of twenty-six halogenated methanes, silanes and germanes of symmetry C_3v and C_2v are reported. Correlations have been found between the primary force constants and the nature of the central atom and of the halogen, and the number of attached halogen atoms. Relationships have also been confirmed between the force and compliance constants and the bond lengths and strengths.     

Determination of net atomic charges using a modified partial equalization of orbital electronegativity method. III. Application to halogenated and aromatic molecules

The net atomic charge parameters for halogen atoms and the atoms in aromatic molecules have been determined by the modified partial equalization of orbital electronegativity method. The same parameters are used for the halogen atoms both in aromatic and nonaromatic systems. The calculated dipole moments of haloalkanes agree well with experiment, but those of the halogenated aromatic molecules do not reproduce the experimental values as well as those of the haloalkanes; in particular, the computed dipole moments for monohalogenated benzenes are all lower than the experimental values because of the influence of the lonepair electrons on the halogens. Within the limitations of an atom-centered point-charge approximation, our calculated dipole moments, both for haloalkanes and halogented aromatic molecules, agree well with experimental values. © John Wiley & Sons, Inc.     

An overlay calculation of the molecular force field of 2- and 3-halogeno derivatives of thiophene

A normal mode calculation, which includes force constants, vibration mean amplitudes, Coriolis parameters and thermodynamic properties, has been performed on a series of six halogenated thiophenes. The zeroth-order force field we have used is that of the thiophene parent molecule, and some specific force constants and interaction constants have been refined using the overlay technique. Results show that the halogen substitution acts upon the heterocyclic ring motion frequencies as an isotopic substitution, viz. with small electronic effects but with remarkable mass effects.     

Effect of quenching time and quenching agent dose on total organic halogen measurement

Total organic halogen (TOX) is a collective parameter and a toxicity indicator for all the halogenated organic disinfection byproducts (DBPs) in a water sample. TOX measurement involves concentration of halogenated organic DBPs by adsorption onto activated carbon. Prior to activated carbon adsorption, quenching the chlorine residual in a water sample is an indispensable step to eliminate the positive interference resulting from continued chlorination with organic compounds adsorbed on the activated carbon surface or with the activated carbon surface itself. Arsenite is generally applied as the quenching agent. In this study, the arsenite quenching agent dose that was 100% of the stoichiometric amount of the chlorine residual in a water sample was demonstrated to be most appropriate. In practice, to ensure complete reduction of chlorine residual, slight overdose of arsenite is often recommended, but this was found to cause negative interferences in the TOX measurement due to two reasons. First, the competitive adsorption existed between halogenated organic DBPs and the excessive arsenite on the activated carbon. This competitive adsorption effect was pronounced within a quenching time of 15?min. After 15?min of quenching, a large fraction of arsenite might have reacted with some easily-reduced halogenated DBPs to become arsenate, which is partially ionized at pH 2 and less likely adsorbed on the activated carbon. In this case, more halogenated organic DBPs could be adsorbed on the activated carbon, resulting in the measured TOX concentrations to be much closer to the actual one contained in the sample. Second, excessive arsenite might lead to reduction or decomposition of halogenated organic DBPs with a prolonged quenching time (>60?min). Thus, to avoid the negative interferences, the appropriate quenching time should be 15–60?min.     

Position dependent heavy atom effect in physical triplet quenching by electron donors

The radical yields and rate constants in the quenching reaction of thionine triplet with the complete series of monohalogen substituted anilines as electron donors were determined by flash spectroscopy. Whereas the quenching rate constants show little and unsystematic variation, the radical yields decrease with increasing spin—orbit coupling constant of the halogen substituent. This effect is very sensitive to the position of the halogen in the donor. The results are explained in terms of a heavy atom effect on the intersystem crossing rate constant in a triplet exciplex.     

Molecular surface electrostatic potentials in the analysis of non-hydrogen-bonding noncovalent interactions

Electrostatic potentials computed on molecular surfaces are used to analyse some noncovalent interactions that are not in the category of hydrogen bonding, e.g. “halogen bonding”. The systems examined include halogenated methanes, substituted benzenes,s-tetrazine and l,3-bisphenylurea. The data were obtained byab initio SCF calculations.     

Effect of halogenated fluorescent compounds on bioluminescent reactions

The paper investigates an application of luminescent bioassays to monitor the toxicity of organic halides. Effects of xanthene dyes (fluorescein, eosin Y, and erythrosin B), used as model compounds, on bioluminescent reactions of firefly Luciola mingrelica, marine bacteria Photobacterium leiognathi, and hydroid polyp Obelia longissima were studied. Dependence of bioluminescence quenching constants on the atomic weight of halogen substituents in dye molecules was demonstrated. Bacterial bioluminescence was shown to be most sensitive to heavy halogen atoms involved in molecular structure; hence, it is suitable for construction of sensors to monitor toxicity of halogenated compounds. Mechanisms of bioluminescence quenching—energy transfer processes, collisional interactions, and enzyme–dye binding—were considered. Changes of bioluminescence (BL) spectra in the presence of the dyes were analyzed. Interactions of the dyes with enzymes were studied using fluorescence characteristics of the dyes in steady-state and time-resolved experiments. The dependences of fluorescence anisotropy of enzyme-bound dyes, the average fluorescence lifetime, and the number of exponential components in fluorescence decay on the atomic weight of halogen substituents were demonstrated. The results are discussed in terms of “dark effect of heavy halogen atom” in the process of enzyme–dye binding; hydrophobic interactions were assumed to be responsible for the effect.     

Study of the Complexation of Octakis(diethoxyphosphoryloxy)-tetramethylcalix[4]resorcinarene with Benzene Derivatives by the RP HPLC Method

Stability constants of the host–guest complexes of octakis(diethoxyphosphoryloxy) tetramethylcalix[4]resorcinarene (RA) with different benzene derivatives (alkyl benzenes, halogenated benzenes, substituted aldehydes, phenols and benzoic acids) were determined by the reversed phase high-performance liquid chromatography (RP HPLC) method (Separon SGX C 18, UV detector at 254 nm and acetonitrile-water, 86 : 14, v/v, as mobile phase) from the relationship between the aromatic guest capacity factors and the RA host concentration in the mobile phase. The constants are within the range 17–596 M^–1, dependent on the size, nature, position and quantity of the substituents in the benzene ring of the guest molecules.     

Aromatic polyamides. XI. Effect of the halogen substitution on the thermal and flammability behavior of poly(1,4-phenylene terephthalamide)

This article concerns the synthesis and characterization of poly(1,4-phenylene terephthalamide) and halogenated derivatives thereof. It was found that the halogen substitution affected significantly the thermal characteristic and flame resistance of that polyamide. In a nonoxygen atmosphere two-step decomposition process for the halogenated, while only one-step for unsubstituted polyamides were observed. The results supported the previous suggestion, that in the case of the halogenated polyamides the char yield enhancement and the flame resistance improvement are associated with halogen release and ring-forming reactions during their pyrolysis.     

Halogen bonding in ligand-receptor systems in the framework of classical force fields

Halogen bond is an important non-covalent interaction which is receiving a growing attention in the study of protein-ligand complexes. Many drugs are halogenated molecules and it has been recently shown that many halogenated ligands establish halogen bonds with biomolecules. As the halogen bond nature is due to an anisotropy of the electrostatic potential around halogen atoms, it is not possible to use traditional force fields based on a set of atom-centred charges to study halogen bonds in biomolecules. We show that the introduction of pseudo-atoms on halogens permits us to correctly describe the anisotropy of the electrostatic potential and to perform molecular dynamics simulations on complexes of proteins with halogenated ligands that reproduce experimental values. The results are compared with crystallographic data and with hybrid quantum mechanics/molecular mechanics calculations.     

Mechanisms of photoinitiated cleavage of DNA by 1,8-naphthalimide derivatives.

Using water-soluble 1,8-naphthalimide derivatives, the mechanisms of photosensitized DNA damage have been elucidated. Specifically, a comparison of rate constants for the photoinduced relaxation of supercoiled to circular DNA, as a function of dissolved halide, oxygen and naphthalimide concentration, has been carried out. The singlet excited states of the naphthalimide derivatives were quenched by chloride, bromide and iodide. In all cases the quenching products were naphthalimide triplet states, produced by induced intersystem crossing within the collision complex. Similarly, the halides were found to quench the triplet excited state of the 1,8-naphthalimide derivatives by an electron transfer mechanism. Bimolecular rate constants were < 10(5) M-1 s-1 for quenching by bromide and chloride. As expected from thermodynamic considerations quenching by iodide was 6.7 x 10(9) and 8.8 x 10(9) M-1 s-1 for the two 1,8-naphthalimide derivatives employed. At sufficiently high ground-state concentration self-quenching of the naphthalimide triplet excited state also occurs. The photosensitized conversion of supercoiled to circular DNA is fastest when self-quenching reactions are favored. The results suggest that, in the case of 1,8-naphthalimide derivatives, radicals derived from quenching of the triplet state by ground-state chromophores are more effective in cleaving DNA than reactive oxygen species or radicals derived from halogen atoms.     

Determination of chlorinated and brominated micropollutants by capillary gas chromatography coupled with on-column radio frequency plasma atomic emission detection

Capillary gas chromatography (GC) combined with on-column radio frequency plasma atomic emission detection was evaluated for the determination of polychlorinated and polybrominated biphenyls (PCBs and PBBs). Quantitation was possible utilizing a single chlorine or bromine calibration curve based on a randomly selected reference compound, because the signal per ng of halogen ranged within 17 % for 29 congeners. Combined with an internal standard to correct for potential plasma quenching from matrix components, this type of universal quantitation represented a sub-stantial simplification of current calibration procedures. In combi-nation with relatively low detection limits (1–5 pg/s of halogen), the present work suggested that GC, coupled with on-column atomic emission detection is a promising technique for the determination of halogenated micropollutants.     

The element effect and nucleophilicity in nucleophilic aromatic photosubstitution (SN2Ar*). Local atom effects as mechanistic probes of very fast reactions

Photoreactions of 4-nitroanisole and the 2-halo-4-nitroanisoles (halogen = F, Cl, Br, and I) with the nucleophiles hydroxide ion and pyridine have been investigated quantitatively to extend the findings recently communicated for cyanide ion. The halonitroanisoles on excitation form triplet pi,pi* states, which undergo substitution of the halogen by nucleophiles. Chemical yields of photoproducts, Stern-Volmer kinetic plots, triplet lifetimes, and triplet yields are reported for the five compounds with the three nucleophiles. Following a standard kinetic treatment, 73 rate constants are determined for elementary reactions of the triplets including quenching and various nucleophilic addition processes. The photoadditions are roughly 14 orders of magnitude faster than thermal counterparts. Rate constants for attack at the fluorine-bearing carbon of triplet 2-fluoro-4-nitroanisole are 2.9 x 10(9), 1.3 x 10(9), and 6.3 x 10(8) M(-1) s(-1) for cyanide ion, hydroxide ion, and pyridine, respectively. The relative rates for attack at the halogen-bearing carbons for F/Cl/Br/I are 27:1.9:1.9:1 (cyanide ion), 29:2.6:2.4:1 (hydroxide ion), and 39:3.9:3.5:1 (pyridine), respectively. The relative nucleophilicities vary somewhat with the attack site; they are about 5:2:1 for cyanide ion, hydroxide ion, and pyridine for attack at the halogen-bearing carbons. The trend of the element effect opposes that of aliphatic substitution and elimination but is similar in size and parallel to that of thermal nucleophilic aromatic substitution. Relative nucleophilicities in the photoreactions are also similar to those of comparable but vastly slower thermal reactions. The findings imply that the efficiency-determining step of the halogen photosubstitution is simple formation of a sigma-complex through electron-paired bonding within the triplet manifold.     

卤代苯溶剂对镓咔咯配合物光物理性质的影响:外重原子效应

利用紫外-可见光谱、稳态和时间分辨荧光光谱以及飞秒瞬态吸收光谱探测了不同卤代苯溶剂对三种五氟苯基取代的镓咔咯(1-Ga、2-Ga、3-Ga)光物理性质的影响,结果表明卤代苯溶剂的色散力对于镓咔咯电子光谱吸收峰位置的影响起着主要作用;溶剂外重原子效应能显著降低镓咔咯的荧光量子产率。飞秒瞬态吸收光谱表明,光激发下,镓咔咯与卤代苯溶剂之间可发生电子转移反应,溶剂的重原子效应可以减缓电荷分离态复合物电荷重组速率。     

Selectivity comparisons of monolithic silica capillary columns modified with poly(octadecyl methacrylate) and octadecyl moieties for halogenated compounds in reversed-phase liquid chromatography

Stationary phase selectivities for halogenated compounds in reversed-phase HPLC were compared using C18 monolithic silica capillary columns modified with poly(octadecyl methacrylate) (ODM) and octadecyl moieties (ODS). The preferential retention of halogenated benzenes on ODM was observed in methanol/water and acetonitrile/water mobile phases. In selectivity comparison of selected analytes on ODM and ODS, greater selectivities for halogenated compounds were obtained with respect to alkylbenzenes on an ODM column, while similar selectivities were observed with a homologous series of alkylbenzenes on ODM and ODS columns. These data can be explained by greater dispersive interactions by more densely packed octadecyl groups on the ODM polymer coated column together with the contribution of carbonyl groups in ODM side chains. For the positional isomeric separation of dihalogenated benzenes (ortho-, meta-, para-), the ODM column also provided better separation of these isomers for the adjacently eluted isomers that cannot be completely separated on an ODS column in the same mobile phase. These results imply that the ODM column can be used as a better alternative to the ODS column for the separation of other halogenated compounds.     

CO2 capture through halogen bonding: A theoretical perspective

Halogen bonding interactions between several halogenated ion pairs and CO2 molecules have been investigated by means of density functional theory calculations. To account for the influence of solvent environment, the implicit polarized continuum model was also employed. The bromide and iodide cations of ionic liquids (ILs) under study can interact with CO2 molecules via X O interactions, which become much stronger in strength than those in the complexes of iodo-perfluorobenzenes, very effective halogen bond donors, with CO2 molecules. Such interactions, albeit somewhat weaker in strength, are also observed between halogenated ion pairs and CO2 molecules. Thus, the solubility of CO2 may be improved when using halogenated ILs, as a result of the formation of X O halogen bonds. Under solvent effects, the strength of the interactions tends to be weakened to some degree, with a concomitant elongation of intermolecular distances. The results presented here would be very useful in the design and synthesis of novel and potent ILs for CO2 physical absorption.     

单次碰撞条件下Ar(3P0.2)与SO2,SOCl2的传能反应

利用化学发光方法研究了Ar（3P0,2）与SO2，SOCl2在单次碰撞条件下SO（A）的形成动力学，通过对实验光谱进行曲线拟会，得到了SO（A，υ＇）的初生态布居．分别是N0：N1：N2：N3：N4：N5：N6＝1．00：0．67：0．57：0．55：0．50：0．35：0．30和1．00：0．69：0．61：0．53：0．40：0．34：0．26．利用参考反应法求算了SO（A）的形成速率，分别为：4．55×10－12cm3•molecule－1•s－1和2．87×10－12cm3•molecule－1•s－1，与总猝灭速率相比较，发现解离激发为反应的次要出口通道．通过惊奇度分析，对激发解离机理进行了讨论．     

Stability of some aryllithiums in the presence of cyano group: synthesis of biaromatic cyanoarylboronic acids and silanes

Lithium diisopropylamine (LDA)‐mediated deprotonation reactions of halogenated cyanobenzyloxy‐benzenes and cyanobiphenyls were investigated. The resultant organolithium derivatives were converted into the corresponding arylboronic acids or silanes. It was found that the stability of the obtained aryllithiums towards isomerization to the respective benzyllithiums depends strongly on the number of fluorine atoms in the phenyl ring and on the position of the cyano group. Halogenated cyanobiaryls were selectively deprotonated in the position flanked by two halogen atoms; however, the yield depended strongly on the reaction conditions. Addition of LDA to the cyano group was observed on the lithiation of 4‐cyano‐3′,5′‐dichlorobiphenyl rather than deprotonation. Copyright © 2012 John Wiley & Sons, Ltd.     

Impact of halogen substituents on interactions between 2-phenyl-2,3-dihydroqulinazolin-4(1H)-one derivatives and human serum albumin

A novel type of 2-(un)substituted phenyl-2,3-dihydroquinazolin-4(1H)-one (DQL) derivatives were designed and synthesized to study the impact of halogen substituents on interactions between DQL and human serum albumin (HSA) by comparison methodology. The interactions between DQL and HSA were studied by fluorescence spectroscopy. The intrinsic fluorescence of human serum albumin was quenched by DQL through a static quenching mechanism. Site marker competitive experiments showed that DQL bound to HSA in site II (subdomain IIIA). The binding constants, the numbers of binding sites and the thermodynamic parameters were measured too. The results indicated that the interactions were spontaneous, mainly through hydrophobic forces, and the substitution by halogen atoms in the benzene ring could increase the interactions between DQL and HSA. Furthermore, the binding affinity was enhanced gradually with the increasing of halogen atomic number.