Spectroelectrochemistry of a photochromic [2.2]paracyclophane-bridged imidazole dimer: clarification of the electrochemical behavior of HABI

The photochromic behavior of the imidazole dimers can be attributable to the photoinduced homolytic cleavage of the C-N bond between the two imidazole rings. On the other hand, although the simultaneous formation of the imidazolyl radical and imidazole anion by the one-electron reduction of an imidazole dimer was reported, no definitive evidence for this electrochemical reaction has been demonstrated. We report the first direct evidence for the electrochemical generation of the imidazolyl radical from the radical anion of the imidazole dimer by conducting the UV-vis-NIR spectroelectrochemical analysis of the [2.2]paracyclophane-bridged imidazole dimer.     

Photochromic properties of [2.2]paracyclophane-bridged imidazole dimer with increased photosensitivity by introducing pyrenyl moiety

The photochromic [2.2]paracyclophane-bridged imidazole dimers show instantaneous coloration upon exposure to UV light and rapid fading in the dark. A new [2.2]paracyclophane-bridged imidazole dimer, pseudogem-PPI-DPI[2.2]PC, with high photosensitivity to UVA radiation was developed. To enhance the photosensitivity, we introduced pyrenyl moieties to the [2.2]paracyclophane-bridged imidazole dimer. The localized π-π* transition of pyrenyl moieties appears in the UVA radiation region by introducing a pyrenyl moietiy on the 4-position of the imidazole rings. The expansion of the π-electron system also affects the absorption spectrum of the colored species. The broad absorption band of the colored species covers the whole range of visible light region and its absorbance is approximately equal throughout the visible light region. Thus, pseudogem-PPI-DPI[2.2]PC shows the photochromic reaction coloring black upon light irradiation and successive fast thermal bleaching following the monoexponential kinetics with a time constant of 12 ms at room temperature.     

Photochromism of a water-soluble vesicular [2.2]paracyclophane-bridged imidazole dimer

Here we report the first photochromism of a newly designed [2.2]paracyclophane-bridged imidazole dimer in water. The photochromic dye with a hydrophilic and a hydrophobic substituent forms vesicles in water and shows instantaneous colouration upon UV light irradiation and successive rapid fading in the dark.     

Lophine derivatives as versatile analytical tools

Lophine (2,4,5-triphenylimidazole) derivatives as versatile analytical tools in biomedical sciences are described. Chemiluminescence (CL) and fluorescence (FL) properties of the lophine derivatives are first demonstrated including the CL reaction mechanism, effects of substituents on CL yields, FL spectral behaviors, etc. Next, analytical applications to the determination of metal ions such as cobalt (II) and chromium (VI) are discussed. Finally, the application studies of lophine derivatives as CL and FL reagents for the determination of organic substances in biological materials are presented. Among the derivatives, 2-(4-hydrazinocarbonylphenyl)-4,5-diphenylimidazole (HCPI) and 4-(4,5-diphenyl-1H-imidazol-2-yl)benzoyl chloride (DIB-Cl) are studied, with their excellent properties as labeling reagents for fatty acids and amines and/or phenols, respectively, in high-performance liquid chromatography. The utility of boronic acid derivatives as CL enhancers is also discussed in this review.     

Infrared laser spectroscopy of imidazole complexes in helium nanodroplets: monomer, dimer, and binary water complexes

Infrared laser spectroscopy has been used to characterize imidazole (IM), imidazole dimer (IMD), and imidazole-water (IMW) binary systems formed in helium nanodroplets. The experimental results are compared with ab initio calculations reported here. Vibrational transition moment angles provide conclusive assignments for the various complexes studied here, including IM, one isomer of IMD, and two isomers of the IMW binary complexes.     

2-Trifluoromethylimidazole, 2,4,5-tris (trifluoromethyl)imidazole and related compounds

2-Trifluoromethylimidazole, prepared by the reaction of imidazole-2-carboxylic acid with sulphur tetrafluoride, afforded a silver salt which reacted with organohalides (bromomethane, ethyl bromoacetate, N,N-dimethyl-2-chloroethylamine, and chloroacetonitrile) to give the corresponding N-alkylated derivatives. 2-Trifluoromethylimidazole-4,5-dicarboxylic acid was obtained by oxidation of 2-trifluoromethylbenzimidazole, and on decarboxylation gave only traces of 2-trifluoromethylimidazole; the major product was 2-trifluoromethylimidazole- 4-carboxylic acid. The di-acid and sulphur tetrafluoride gave 2,4,5-tris (trifluoromethyl) imidazole.     

Ab initioSCF MO calculations on the reactions of hydroxyl radical with imidazole and monoprotonated imidazole

The addition reactions of hydroxyl radical with imidazole and its protonated form to yield radical adducts have been investigated by ab initio SCF MO methods using STO -3G and 4-31G basis sets. Analogous radical species are of importance in radiation damage to biological systems. Of the possible radical products, the calculations indicate that the allylic species are generally favored energetically over the nonallylic forms. On an energetic basis, the results show that the allylic adducts formed by addition at the C2 and C5 positions are about equally favorable. Although the C5 species is generally identified as the experimentally observed product in aqueous media for both protonated and unprotonated imidazole, some experimental evidence exists indicating the presence of other forms. Our results suggest that this other form is the C2 adduct. The calculations also point to the protonated form of imidazole being less reactive than imidazole, which is in accord with experimental observations.     

Coupling properties of imidazole dimer radical cation assisted by embedded water molecule: toward understanding of interaction character of hydrogen-bonded histidine residue side-chains

Geometry optimizations are performed at the DFTB3LYP6-311+G* level. Four intriguing coupling modes, totally eight stable structures are found in the potential energy surfaces of the water-assisted coupling of imidazole dimer radical cation. In these isomers, the water molecules are embedded between two imidazole moieties, and the oxygen atom is tridentate or quadridentate, respectively. The distinct redshifts of the vibrational frequencies of the O-H...N and N-H...O type H bonds indicate the strong interaction of two imidazole rings of respective isomer. Inspection of the highest occupied molecular orbital predicts the alterations of the geometry structures on oxidation and reduction. The low barrier of the fragment rotation demonstrates that the isomerization processes by experiencing the distinct transition states are easy to fulfill, especially for those with O-H...N and C-H...O H bonds. Both the energy difference of the 0 degrees-cis and 180 degrees-trans orientation and the barriers of the fragment rotation are lowered by the water assisting. The range of the zero point vibrational energy correction indicates that the influence on the complexes with N-H...O and O-H...N H bonds (0.13-0.17 kcal/mol) is more significant than those with O-H...N and C-H...O H bonds (+/-0.03 kcal/mol). The dissociation energies of these isomers indicate that the charges transfer easily through water in the dissociation process and then are distributed mainly over the imidazole ring connecting with water molecule. The isomer with proton transfer between imidazole fragments is the most stable one.     

Application of the νD/νH ratio to the assignment of C-H(D) and ring vibrations in the infrared spectra of imidazole and its deuterated analogues

The IR spectra (4000-150 cm^?1)of imidazole and its I-, 2,4,5- and 1,2,4,5-deuterated analogues are discussed. All twenty-one fundamental IR active imidazole vibrations are assigned by employing the ν^D/ν^H ratio which is defined as the ratio between the frequencies of corresponding IR bands in the spectra of a ring-deuterated heterocyclic (or aromatic) molecule and its normal analogue. The results suggest that some previously reported assignments require revision.     

2,4,5‐Tri­phenyl‐4H‐imidazol‐4‐yl hydro­peroxide–di­chloro­methane (2/1)

The structure of lophine peroxide was confirmed to be 2,4,5‐tri­phenyl‐4H‐imidazol‐4‐yl hydro­peroxide and not the 2,5‐endoperoxide. The asymmetric unit is composed of an O—H?N hydrogen‐bonded dimer of lophine peroxide with an R/R or S/S configuration and a CH₂Cl₂ solvent mol­ecule, i.e. 2C₂₁H₁₆N₂O₂·CH₂Cl₂.     

Water-soluble supramolecular porphyrin dimer: self-organization of mono(imidazolyl)-substituted Zn porphyrin to a special-pair type dimer in water

Tris(4-carboxylphenyl)-mono(N-methylimidazolyl)-substituted Zn porphyrin was synthesized as a precursor for a water-soluble supramolecular porphyrin dimer. The dimer formation was performed in a NaHCO₃ aq solution (pH 8.4) and phosphate buffer solutions (pH 7.4-9.0). The split Soret bands of Zn porphyrin observed in the absorption spectra clearly showed self-organization to a special-pair type slipped cofacial dimer via metal coordination of imidazole even in water.     

Highly efficient and metal-free synthesis of tri- and tetrasubstituted imidazole catalyzed by 3-picolinic acid

3-Picolinic acid is an efficient organo-catalyst for a one-pot three-component synthesis of 2,4,5-triaryl substituted imidazole. Moreover, the utility of this catalyst has been extended to the four-component synthesis of 1,2,4,5-tetra-substituted imidazole. The pivotal advantages of this process are easy purification, cost-effectiveness, and high yielding, above all environmentally benign protocol.     

Semiconductor photoinduced cycloreversion of the dimer of methyl 2-naphthoate

The dimer of methyl 2-naphthoate (1) has been found to undergo efficient cyclorever-sion to its monomer, methyl naphtha)ene-2-carboxylate (2) on illuminated ZnO and TiO2 but not on CdS. An electron transfer and cation radical chain mechanism is proposed. Quantum yields, solvent effect, the role of oxygen, and the quenching of the reaction were investigated, and were consistent with the proposed mechanism.     

Ring opening of the cyclobutane in a thymine dimer radical anion

The reactions of hydrated electrons (e(aq) (-)) with thymine dimer 2 and thymidine have been investigated by radiolytic methods coupled with product studies, and addressed computationally by means of BB1K-HMDFT calculations. Pulse radiolysis revealed that one-electron reduction of the thymine dimer 2 affords the radical anion of thymidine (5) with t(1/2)<35 ns. Indeed, the theoretical study suggests that radical anion 3, in which the spin density and charge distribution are located in both thymine rings, undergoes a fast partially ionic splitting of the cyclobutane with a half-life of a few ps. This model fits with the in vivo observation of thymine dimer repair in DNA by photolyase. gamma-Radiolysis of thymine dimer 2 demonstrates that the one-electron reduction and the subsequent cleavage of the cyclobutane ring does not proceed by means of a radical chain mechanism, that is, in this model reaction the T(-)* is unable to transfer an electron to the thymine dimer 2.     

Oxidation products of 2-arylphenanthro-[9,10-d]imidazoles—II : Structure and photochromism of oxidation products of 2-(4-methoxyphenyl)-phenanthro-[9,10-d]imidazole

By ferricyanide oxidation of 2-(4-methoxyphenyl)phenanthro[9,10-d]imidazole, three new photochromic compounds were obtained. These were 4-ethoxy-4H-, 4-methoxy-4H- and 2-methoxy-2H-phenanthro[9,10-d]imidazoles. These compounds gave the 2-(4-methoxyphenyl)-phenanthro[9,10-d]imidazolyl radical and acetaldehyde or formaldehyde by light irradiation. The imidazolyl radical dimerized gradually in the dark and the dimer dissociated to the imidazolyl radical on heating.     

Formation of intramolecular poly(4-hydroxystyrene) dimer radical cation

Poly(4-hydroxystyrene) (PHS) has been used in lithography as a backbone polymer and is also a promising material for extreme-ultraviolet or electron beam lithography. The dynamics of PHS radical cations generated upon exposure to electron beam were investigated. The transient absorption of PHS was observed in the near-infrared region in p-dioxane solutions by pulse radiolysis. Charge resonance (CR) bands that represent pi-pi interaction between the two chromophores of the intramolecular PHS dimer radical cation were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that the dimer radical cation formation leads to less deprotonation by its charge resonance stabilization.     

Simple dimer containing dissociatively stable mono-imidazole ligated ferrohemes

In weakly coordinating solvents FeII meso-(N-methylimidazol-2-yl)porphine Fe exists as a stable dimer (Kd=50+/-30 nM) that binds ligands without undergoing dissociation and is presently the simplest complex in which the mono-imidazole ligation of a ferroheme is enforced without excess imidazole in solution.     

Synthesis of fused tetrazole- and imidazole derivatives via iodocyclization

The possibility to prepare fused tetrazole- and imidazole derivatives by iodocyclization in moderate to excellent yields is demonstrated. In some examples the cyclizations were not following Baldwin's rules entirely, i.e. exo-selectivity. Nucleophilic substitution of the formed iodides gave different results depending on the hardness of the nucleophile. Thus, elimination of the iodide could be a problem but a substitution reaction with ethyl potassium xanthate and a radical reaction using acrylonitrile were tolerated. In addition, we showed that it is possible to selectively use three iodo substituents individually in one of the fused imidazole derivatives.     

Studies on the effects of imidazole on the peroxyoxalate chemiluminescence detection system for high performance liquid chromatography

The catalytic effect of bases (imidazole, pyridine, Tris and triethylamine) on the peroxyoxalate chemiluminescence (PO-CL) reaction for high performance liquid chromatography (HPLC) was investigated. Imidazole increased PO-CL intensity extraordinarily, whereas the other bases (pyridine, Tris and triethylamine) did not. The peak heights of dipyridamole (coronary vasodilator) obtained using the eluents containing buffers were largest at pH 7.0, a few times less at pH 6.0 and pH 5.0, 100 times less at pH 4.0 and a few hundred times less at pH 3.0. The eluents containing buffers at pH 3, 4, 5, 6 or 7 each with imidazole increased the peak heights by a few to ten times as compared with those without imidazole, and those peak heights were within one order of magnitude. On the other hand, the eluent containing buffer at pH 2 did not affect the peak heights with or without imidazole. Bis(4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl) oxalate (TDPO) alone and bis(2,4-dinitrophenyl)oxalate (DNPO) plus TDPO were recommended to be used against eluents containing buffers of pH 5-7 and pH 3-4, respectively. Dipyridamole and benzydamine hydrochloride (anti-inflammatory drug) were separated on the ODS column and detected by the present system. The detection limits of dipyridamole and benzydamine hydrochloride were 40 amol and 270 fmol, respectively.     

Reaction pathways to dimer in polystyrene pyrolysis: A mechanistic modeling study

A detailed mechanistic model for polystyrene pyrolysis was created that built on a modeling framework developed in our previous work and was used to probe three competing pathways to dimer formation: benzyl radical addition, 1,3-hydrogen shift, and 7,3-hydrogen shift, based on recent literature reports. To incorporate the chemistry involved in the 7,3-hydrogen shift pathway, the 1,7- and 7,3-hydrogen shift reaction families were added to the model. The updated version of the model tracks 75 species and over 3500 reactions. Rate parameters for all families were specified based on our previous work, more recent literature reports, and regression against limited experimental data. The model was able to accurately predict the experimental results for polystyrene pyrolysis for different reactor configurations for a temperature range of 100 °C and two orders of magnitude of initial molecular weight for experimental data collected in our own lab and from Bouster and coworkers and Bockhorn and coworkers. The results from our model were studied using net rate analysis to gain insight into the competitiveness of the various reaction pathways to dimer formation. The net rate analysis demonstrated that 7,3-hydrogen shift is the dominant reaction pathway to dimer formation at the temperatures studied. Benzyl radical addition becomes a more competitive reaction pathway as the temperature increases, which is caused predominantly by an increase in the benzyl radical concentration with increasing temperature. Overall, it is quantitatively shown that both 7,3-hydrogen shift and benzyl radical addition are important pathways for dimer formation, with their relative competitiveness influenced by temperature.