Kinetic study of the hydrogen abstraction reaction of the benzotriazole-N-oxyl radical (BTNO) with H-donor substrates

[Reaction: see text]. The aminoxyl radical (>N-O*) BTNO (benzotriazole-N-oxyl) has been generated by the oxidation of 1-hydroxybenzotriazole (HBT; >N-OH) with a Ce(IV) salt in MeCN. BTNO presents a broad absorption band with lambda(max) 474 nm and epsilon 1840 M(-1) cm(-1), and spontaneously decays with a first-order rate constant of 6.3 x 10(-3) s(-1) in MeCN at 25 degrees C. Characterization of BTNO radical by EPR, laser flash photolysis, and cyclic voltammetry is provided. The spontaneous decay of BTNO is strongly accelerated in the presence of H-donor substrates such as alkylarenes, benzyl and allyl alcohols, and alkanols, and rate constants of H-abstraction by BTNO from a number of substrates have been spectroscopically investigated at 25 degrees C. The kinetic isotope effect confirms the H-abstraction step as rate-determining. Activation parameters have been measured in the 15-40 degrees C range with selected substrates. A correlation between E(a) and BDE(C-H) (C-H bond dissociation energy) for a small series of H-donors has been obtained according to the Evans-Polanyi equation, giving alpha = 0.44. From this plot, the experimentally unavailable BDE(C-H) of benzyl alcohol can be extrapolated, as ca. 79 kcal/mol. With respect to the H-abstraction step, peculiar differences in the DeltaS++ parameter emerge between an alkylarene, ArC(H)R2, and a benzyl alcohol, ArC(H)(OH)R. The data acquired on the H-abstraction reactivity of BTNO are compared with those recently reported for the aminoxyl radical PINO (phthalimide-N-oxyl), generated from N-hydroxyphthalimide (HPI). The higher reactivity of radical PINO is explained on the basis of the higher energy of the NO-H bond of HPI, as compared with that of HBT (88 vs ca. 85 kcal/mol, respectively), which is formed on H-abstraction from the RH substrate.     

Chemoselective C-4 aerobic oxidation of catechin derivatives catalyzed by the Trametes villosa laccase/1-hydroxybenzotriazole system: synthetic and mechanistic aspects

Catechin derivatives were oxidized in air in the presence of the Trametes villosa laccase/1-hydroxybenzotriazole (HBT) system in buffered water/1,4-dioxane as reaction medium. The oxidation products, flavan-3,4-diols and the corresponding C-4 ketones, are bioactive compounds and useful intermediates for the hemisynthesis of proanthocyanidins, plant polyphenols which provide beneficial health properties for humans. Determinations of oxidation potentials excluded that catechin derivatives could be directly oxidized by laccase Cu(II), while it resulted in the H-abstraction from benzylic positions being promptly promoted by the enzyme in the presence of the mediator HBT, the parent species producing in situ the reactive intermediate benzotriazole-N-oxyl (BTNO) radical. A remarkable and unexpected result for the laccase/HBT oxidative system has been the chemoselective insertion of the oxygen atom into the C-4-H bond of catechin derivatives. Mechanistic aspects of the oxidation reaction have been investigated in detail for the first time in order to corroborate these results. Since the collected experimental findings could not alone provide information useful to clarify the origin of the observed chemoselectivity, these data were expressly supplemented with information derived by suitable molecular modeling investigations. The integrated evaluation of the dissociation energies of the C-H bonds calculated both by semiempirical and DFT methods and the differential activation energies of the process estimated by a molecular modeling approach suggested that the observed selective oxidation at the C-4 carbon has a kinetic origin.     

One-electron oxidation of ferrocenes by short-lived N-oxyl radicals. The role of structural effects on the intrinsic electron transfer reactivities

A kinetic study of the one electron oxidation of substituted ferrocenes (FcX: X = H, COPh, COMe, CO(2)Et, CONH(2), CH(2)OH, Et, and Me(2)) by a series of N-oxyl radicals (succinimide-N-oxyl radical (SINO), maleimide-N-oxyl radical (MINO), 3-quinazolin-4-one-N-oxyl radical (QONO) and 3-benzotriazin-4-one-N-oxyl radical (BONO)), has been carried out in CH(3)CN. N-oxyl radicals were produced by hydrogen abstraction from the corresponding N-hydroxy derivatives by the cumyloxyl radical. With all systems, the rate constants exhibited a satisfactory fit to the Marcus equation allowing us to determine self-exchange reorganization energy values (λ(NO˙/NO(-))) which have been compared with those previously determined for the PINO/PINO(-) and BTNO/BTNO(-) couples. Even small modification of the structure of the N-oxyl radicals lead to significant variation of the λ(NO˙/NO(-)) values. The λ(NO˙/NO(-)) values increase in the order BONO < BTNO < QONO < PINO < SINO < MINO which do not parallel the order of the oxidation potentials. The higher λ(NO˙/NO(-)) values found for the MINO and SINO radicals might be in accordance with a lower degree of spin delocalization in the radicals MINO and SINO and charge delocalization in the anions MINO(-) and SINO(-) due to the absence of an aromatic ring in their structure.     

Isomeric structures of benzimidazole, benzoxazole, and benzothiazole derivatives, their electronic properties and transformations

The optimized structures of all isomers of HBI, HBO, HBT, HPyBI, HPyBO, and HPyBT compounds were obtained using the potential energy surface method at the B3LYP/6-311++G(d,p) level of theory. Four isomers and three transition states of their transformations for each compound of HBO, HBT, HPyBO, and HPyBT and two isomers and one transition state for each HBI and HPyBI compounds were found. Energetics, thermodynamic properties, rate constants, and equilibrium constants of their transformations were determined. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The effect of hydrogen bonding on the excited-state proton transfer in 2-(2'-hydroxyphenyl)benzothiazole: a TDDFT molecular dynamics study

The dynamics of the excited-state proton transfer (ESPT) in a cluster of 2-(2'-hydroxyphenyl)benzothiazole (HBT) and hydrogen-bonded water molecules was investigated by means of quantum chemical simulations. Two different enol ground-state structures of HBT interacting with the water cluster were chosen as initial structures for the excited-state dynamics: (i) an intramolecular hydrogen-bonded structure of HBT and (ii) a cluster where the intramolecular hydrogen bond in HBT is broken by intermolecular interactions with water molecules. On-the-fly dynamics simulations using time-dependent density functional theory show that after photoexcitation to the S(1) state the ESPT pathway leading to the keto form strongly depends on the initial ground state structure of the HBT-water cluster. In the intramolecular hydrogen-bonded structures direct excited-state proton transfer is observed within 18 fs, which is a factor two faster than proton transfer in HBT computed for the gas phase. Intermolecular bonded HBT complexes show a complex pattern of excited-state proton transfer involving several distinct mechanisms. In the main process the tautomerization proceeds via a triple proton transfer through the water network with an average proton transfer time of approximately 120 fs. Due to the lack of the stabilizing hydrogen bond, intermolecular hydrogen-bonded structures have a significant degree of interring twisting already in the ground state. During the excited state dynamics, the twist tends to quickly increase indicating that internal conversion to the electronic ground state should take place at the sub-picosecond scale.     

Excited-state proton transfer in 2-(2'-hydroxyphenyl)benzothiazole: formation of the anion in polar solvents

Excited-state proton transfer in 2-(2'-hydroxyphenyl)benzothiazole (HBT) dissolved in pyridine is investigated. New absorptions and fluorescence bands are detected after addition of water or NaOH to the solution. The spectra are identical to the HBT anion absorption and fluorescence. Picosecond spectroscopy is used to determine the kinetics of electronically excited states. The excited-state lifetime of the anion is 3.5 ns. The tautomeric fluorescence of HBT after proton transfer builds up within 4 ps after excitation and decays with a time constant of 20 ps.     

Infrared and Raman spectra of 2-(α-hydroxybenzyl)thiamine, 2-(α-hydroxycyclohexylmethyl)thiamine,their protonated forms and their complexes with zinc(II), cadmium(II) and mercury(II)

The infrared and Raman spectra of the ligands; 2-(α-hydroxybenzyl)thiaminium chloride (HBT), 2-(α-hydroxycyclohexylmethyl)thiaminium chloride (HCMT), and their protonated forms HBT·HCl and HCMT·HCl, as well as of their zwitterionic type complexes Zn(HBT)Cl₃, Cd(HBT)Cl₃, Hg(HBT)Cl₃ and Zn(HCMT)Cl₃, Cd(HCMT)Cl₃, Hg(HCMT)Cl₃, have been recorded in the region 4000-50 cm⁻. Several characteristic bands have been identified or tentatively assigned and are discussed in relation to the structures of the complexes. It is concluded from the spectra that the complexes are isostructural and that the bonding site of the ligands is the N(1′) atom of the pyrimidine moiety.     

Photoluminescent mechanism of a proton-transfer laser dye in highly doped polymer films

Photoluminescent properties in thin films of the proton-transfer laser dye, 2-(2-hydroxyphenyl)benzothiazole (HBT) were investigated, when it was doped into hole-transport polymer, poly(N-vinylcarbazole) and when it was codoped with hole-transport small molecule, N,N′-di(m-tolyl)-N,N′-diphenylbenzidine (TPD) into polystyrene. The more the doping concentration of HBT was raised up to about 40 wt%, the more its photoluminescent intensity was enhanced without showing excimer or exciplex emissions. The mechanism for such phenomena was discussed in connection with the excited-state intramolecular proton-transfer reaction of HBT.     

Excited State Intramolecular Proton Transfer in Ethynyl‐Extended Regioisomers of 2‐(2′‐Hydroxyphenyl)benzothiazole: Effects of the Position and Electronic Nature of Substituent Groups

Although the organic dyes based on excited state intramolecular proton transfer (ESIPT) mechanism have attracted significant attention, the structure‐property relationship of ESIPT dyes needs to be further exploited. In this paper, three series of ethynyl‐extended regioisomers of 2‐(2′‐hydroxyphenyl)benzothiazole (HBT), at the 3′‐, 4′‐ and 6‐positions, respectively, have been synthesized. Changes in the absorption and emission spectra were correlated with the position and electronic nature of the substituent groups. Although 4′‐ and 6‐substituted HBT derivatives exhibited absorption bands at longer wavelengths, the keto‐emission of 3′‐substituted HBT derivatives was found at a substantially longer wavelength. The gradual red‐shifted fluorescence emission was found for 3′‐substituted HBT derivatives where the electron‐donating nature of substituent group increased, which was opposite to what was observed for 4′‐ and 6‐substituted HBT derivatives. The results derived from the theoretical calculations were in conformity with the experimental observations. Our study could potentially provide experimental and theoretical basis for designing novel ESIPT dyes that possess unique fluorescent properties.     

Biodegradation of Bisphenol A and Decolorization of Synthetic Dyes by Laccase from White-Rot Fungus, Trametes polyzona

Purified laccase from Trametes polyzona WR710-1 was used as biocatalyst for bisphenol A biodegradation and decolorization of synthetic dyes. Degradation of bisphenol A by laccase with or without redox mediator, 1-hydroxybenzotriazole (HBT) was studied. The quantitative analysis by HPLC showed that bisphenol A rapidly oxidized by laccase with HBT. Bisphenol A was completely removed within 3 h and 4-isopropenylphenol was found as the oxidative degradation product from bisphenol A when identified by GC-MS. All synthetic dyes used in this experiment, Bromophenol Blue, Remazol Brilliant Blue R, Methyl Orange, Relative Black 5, Congo Red, and Acridine Orange were decolorized by Trametes laccase and the percentage of decolorization increased when 2 mM HBT was added in the reaction mixture. This is the first report showing that laccase from T. polyzona is an affective enzyme having high potential for environmental detoxification, bisphenol A degradation and synthetic dye decolorization.     

Acid‐Induced Shift of Intramolecular Hydrogen Bonding Responsible for Excited‐State Intramolecular Proton Transfer

The significant progress recently achieved in designing smart acid‐responsive materials based on intramolecular charge transfer inspired us to utilize excited‐state intramolecular proton transfer (ESIPT) for developing a turn‐on acid‐responsive fluorescent system with an exceedingly large Stokes shift. Two ESIPT‐active fluorophores, 2‐(2‐hydroxyphenyl)pyridine (HPP) and 2‐(2‐hydroxyphenyl)benzothiazole (HBT), were fused into a novel dye (HBT‐HPP) fluorescent only in the protonated state. Moreover, we also synthesized three structurally relevant control compounds to compare their steady‐state fluorescence spectra and optimized geometric structures in neutral and acidic media. The results suggest that the fluorescence turn‐on was caused by the acid‐induced shift of the ESIPT‐responsible intramolecular hydrogen bond from the HPP to HBT moiety. This work presents a systematic comparison of the emission efficiencies and basicity of HBT and HPP for the first time, thereby utilizing their differences to construct an acid‐responsive smart organic fluorescent material. As a practical application, red fluorescent letters can be written using the acid as an ink on polymer film.     

Synthesis and photovoltaic properties of low‐bandgap 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole‐based poly(heteroarylenevinylene)s

Three novel low‐bandgap copolymers containing alkylated 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole (HBT) and different electron‐rich functional groups (dialkylfluorene (PFV‐HBT), dialkyloxyphenylene (PPV‐HBT) and dialkylthiophene (PTV‐HBT)) were prepared by Horner polycondensation reactions and characterized by ¹H NMR, gel permeation chromatography, and elemental analysis. The alkyl side chain brings these polymeric materials good solubility in common organic solvents, which is critical for the manufacture of solar cells in a cost‐effective manner. The copolymers exhibit low optical bandgap from 1.48 to 1.83 eV. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the copolymers were measured by cyclic voltammetry. Theoretical calculations revealed that the variation laws of HOMO and the LUMO energy levels are well consistent with cyclic voltammetry measurement. The bulk heterojunction photovoltaic devices with the structure of ITO/PEDOT‐PSS/polymer:PCBM/LiF/Al were fabricated by using the three copolymers as the donor and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) as the acceptor in the active layer. The device based on PTV‐HBT:PCBM (1:4 w/w) achieved a power conversion efficiency of 1.05% under the illumination of AM 1.5, 100 mW/cm². © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Rational design of the benzothiazole-based fluorescent scaffold for tunable emission

The 2-(2-hydroxyphenyl)-benzothiazole (HBT) fluorophore has attracted considerable attention due to its excited-state intramolecular proton transfer (ESIPT) based emission and its large Stokes shift. However, this fluorophore possesses several disadvantages including low quantum yield and short emission in the blue range. In this study, by coupling HBT at the ortho-, meta-, and para-positions to the hydroxyl group with different heterocycles to extend the conjugation system, we have successfully obtained new fluorophores with tunable emissions both in solution and in the solid-state (409–652?nm). Notably, all of the derivatives demonstrated improved quantum yields compared with the parent HBT structure. Moreover, selected compounds have been shown to shine brightly in live cells, indicating promising potential for bioimaging.     

Ultrafast branching of reaction pathways in 2-(2'-hydroxyphenyl)benzothiazole in polar acetonitrile solution

In a combined study on the photophysics of 2-(2'-hydroxyphenyl)-benzothiazole (HBT) in polar acetonitrile utilizing ultrafast infrared spectroscopy and quantum chemical calculations, we show that a branching of reaction pathways occurs on femtosecond time scales. Apart from the excited-state intramolecular hydrogen transfer (ESIHT) converting electronically excited enol tautomer into the keto tautomer, known to be the dominating mechanism of HBT in nonpolar solvents such as cyclohexane and tetrachloroethene, in acetonitrile solution twisting also occurs around the central C-C bond connecting the hydroxyphenyl and benzothiazole units in both electronically excited enol and keto tautomers. The solvent-induced intramolecular twisting enables efficient internal conversion pathways to both enol and keto tautomers in the electronic ground state. Whereas relaxation to the most stable enol tautomer with twisting angle Θ = 0° implies full ground state recovery, a small fraction of HBT molecules persists as the keto twisting conformer with the twisting angle Θ = 180° for delay times extending beyond 120 ps.     

On the interaction of HBT with pulp lignin during mediated laccase delignification—a study using fractionated pyrolysis-GC/MS

An analytical method using fractionated pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was developed and applied for characterizing the type of interaction between 1-hydroxybenzotriazole (HBT)-mediator and pulp lignin in laccase delignification of pulp. In fractionated pyrolysis, the sample is pyrolyzed at progressively increasing temperatures in order to study particular fractions of the sample and to minimize secondary pyrolysis effects. This makes it possible to determine whether a certain pyrolysis product originates from one chemical moiety or different chemical moieties in one molecule. In the present method, samples were fractionated by thermal desorption at 200 °C followed by pyrolysis at progressively increasing temperatures from 320 to 800 °C. The products formed in each fraction were separated in a capillary GC column and detected and identified using MS. The type of interaction between HBT and pulp lignin was studied by following the formation of nitrogen-containing products during fractionated pyrolysis of a residual lignin isolated from laccase/HBT-treated oxygen-delignified softwood kraft pulp. This residual lignin was found to contain approximately 2% HBT residue. Most (87%) of this residue was covalently linked to the residual lignin. The results also strongly suggest that the HBT residue is present in two chemically different forms.     

Excited State Intramolecular Proton Transfer and Photophysics of a New Fluorenyl Two‐Photon Fluorescent Probe

The steady‐state photophysical, NMR, and two‐photon absorption (2PA) properties of a new fluorene derivative ( 1 ) containing the 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) terminal construct is investigated for use as a fluorescence probe in bioimaging. A comprehensive analysis of the linear spectral properties reveals inter‐ and intramolecular hydrogen bonding and excited state intramolecular proton transfer (ESIPT) processes in the HBT substituent. A specific electronic model with a double minimum potential energy surface is consistent with the observed spectral properties. The 2PA spectra are obtained using a standard two‐photon induced fluorescence method with a femtosecond kHz laser system, affording a maximum 2PA cross section of ～600 GM, a sufficiently high value for two‐photon fluorescence imaging. No dependence of two‐photon absorption efficiency on solvent properties and hydrogen bonding in the HBT substituent is observed. The potential use of this fluorenyl probe in bioimaging is demonstrated via one‐ and two‐photon fluorescence imaging of COS‐7 cells.     

On the mechanism of the laccase-mediator system in the oxidation of lignin

In an effort to elucidate the role of phenolic and non-phenolic lignin subunits in a laccase mediator (LM) system, vanillyl alcohol was oxidized with laccase in the presence and absence of the mediator 1-hydroxybenzotriazol (HBT). Furthermore, the role of phenolic, aliphatic hydroxyl, and carboxylic acid moieties in lignin degradation was elucidated by selectively blocking them. The modified samples were then subjected to laccase and laccase-HBT treatments. On the basis of this data it was possible to establish the role of this mediator. HBT mediates the oxidation of lignin by inducing side-chain oxidation and oxygen-addition products rather than oxidative coupling reactions.     

Janus-Type ESIPT Chromophores with Distinctive Intramolecular Hydrogen-bonding Selectivity

Excited-state intramolecular proton transfer (ESIPT)-based solid luminescent materials with multiple hydrogen bond acceptors (HBAs) remain unexplored. Herein, we introduced a family of Janus-type ESIPT chromophores featuring distinctive hydrogen bond (H-bond) selectivity between competitive HBAs in a single molecule. Our investigations showed that the central hydroxyl group preferentially forms intramolecular H-bonds with imines in imine-modified 2-hydroxyphenyl benzothiazole (HBT) chromophores but tethers the benzothiazole moiety in hydrazone-modified HBT chromophores. Imine-derived HBTs generally exhibit higher fluorescence efficiency, while hydrazone-derived HBTs show a reduced overlap between the absorption and fluorescence bands. Quantum chemical calculations unveiled the molecular origins of the biased intramolecular H-bonds and their impact on the ESIPT process. This Janus-type ESIPT chromophore skeleton provides new opportunities for the design of solid luminescent materials.     

Interactions of metal ions with the intermediate of thiamine catalysis: Crystal structures of Cd(II), Hg(II) and Pt(II) complexes of 2-(α-hydroxybenzyl)thiamine

Five complexes of formulae Cd(HBT)X₃·H₂O, Hg₂X₅(HBT) (X=Cl, Br), and Pt(HBT)(NO₂)₃ were prepared by reacting CdX₂, HgX₂ and K₂Pt(NO₂)₄ with 2-(α-hydroxybenzyl)thiamine (HBT), an active intermediate of thiamine catalysis, and their crystal structures were determined by X-ray diffraction. The metal ion binds to the N(1′) site of the pyrimidine ring in each case, despite the different shapes and sizes of metal coordination units; a tetrahedral unit in the cadmium complexes, a double-metal unit consisting of two tetrahedral Hg(II) ions in the mercury complexes and a square-planar unit in the platinum complex. The HBT ligands in these complexes adopt the S conformation, as usually observed in C(2)-substituted derivatives of thiamine, with average torsion angles ϕ_T being ±99° and ϕ_P being ±175°. A ‘two-point’ anion-bridge between the amino group of the pyrimidine ring and the cationic thiazolium ring of the same molecule is found in all the structures, being of the form N(4′α)–H…X₁–M–X₂…thiazolium-ring (M=metal ion), which is one of the factors that affect the S conformation. Stacking interactions between the pyrimidine and phenyl rings play an important role in the molecular conformation and crystal packing. The intramolecular close contact between the oxygen of the C(2)-substituent and the sulfur of the thiazolium ring is also a common feature to these complexes, which gives the mechanistic implications.     

Simultaneous determination of herbicide mefenacet and its metabolites residues in river water by solid phase extraction and rapid resolution liquid chromatography-mass spectrometry with pre-column derivatization

A procedure based on solid phase extraction (SPE) has been developed for the simultaneous pre-concentration of herbicide mefenacet (MN) and its three photolysis degradation products. Three metabolites studied were hydroxylbenzothiazole (HBT), N-methylaniline (N-MA) and 2-benzothiazoloxyacetic acid (2-BAA). A trimethylsilylation derivatization method was applied for the analysis of HBT and 2-BAA which were derivatized to be corresponding derivatives D-1 and D-2, respectively, and a rapid resolution liquid chromatography-electrospray ionization mass spectrometry (RRLC-ESI-MS) system was used for the separation, identification and quantification of these four analytes. In the SPE pre-concentration step, three types of cartridges and four kinds of eluents were investigated. The mean recoveries of these four analytes were between 78.6% and 101.2% and relative standard deviations were between 3.2% and 9.2%. The limits of detection (LODs) obtained were 0.02 ng l⁻¹ for MN and N-MA and 0.1 ng l⁻¹ for HBT and 2-BAA which were less than the maximum residue limits (MRLs) in drinking water established by European legislation (0.1 μg l⁻¹). The proposed method was applied to evaluate the presence and evolution with time of herbicide mefenacet and its degradation products in samples of Songhuajiang River of Heilongjiang province, China. The analyses, conducted from April to July of 2008, pointed to the presence of MN, 2-BAA, HBT and N-MA at maximum levels 1.0, 0.08, 0.1 and 0.3 μg l⁻¹.