Hyperfine couplings ofN-alkoxy-N-polynitrophenylaminyl radicals determined by ENDOR and TRIPLE resonance spectroscopy

Lead tetraacetate one-electron oxidation of nine different N-alkoxy-2,6-dinitroanilines substituted with trifluoromethyl, methyl and nitro groups in position 4 yielded aminyl radicals for which hyperfine couplings were measured by ENDOR and TRIPLE resonance spectroscopy. The optimum temperature range for proton ENDOR and general TRIPLE resonance measurements of aminyl radicals was 210–250 K and for nitrogen ENDOR 260 K in toluene. Further lowering for the temperature rapidly decreased the EPR intensity. The concentration of the sample and the amount of oxidant were optimized for obtaining ENDOR spectra. The relative signs of the hyperfine couplings of nitrogens, fluorines and protons were d…

Polarity profiles in reverse micelles of Triton X-100, as studied by spin probe and absorption probe techniques

The microenvironment characteristics — polarity, viscosity and order degree - in Triton X-100 reverse micelles (RM) in cyclohexane and benzene — n-hexane 30 : 70 (v/v), were investigated with the aid of a homologous series of cationic spin probes, CAT n, of 5- and 16-doxyl stearic acids and of a new absorption probe, 4-nitropyridine-N-oxide (NP). The spectral parameters were related to local hydration values by means of a series of poly(oxyethylene) (PEO)/water calibration mixtures. All results regarding the polarities in RM and calibration mixtures have been expressed in terms of Kosower's Z values, by determining the linear dependence of the transition energies of NP, ENP, on Z, for a ser…

ESR, ENDOR and TRIPLE resonance studies on radical reactions of 1,4-benzoquinone and 1,4-hydroquinone in alkaline methanol and liquid ammonia

The relative signs and absolute values of the hyperfine coupling constants of different methoxy-1,4-benzoquinones were measured by ESR, ENDOR and TRIPLE resonance spectroscopy. Reactions of 1,4-benzoquinone and 1,4-hydroquinone with methanol took place in alkaline methanol, giving rise to methoxy-substituted 1,4-benzoquinones. The same substitution reaction occurred in a mixture of ammonia and methanol. The reactions depended on temperature and the alkali concentration. Coupling constants were assigned by the modified additivity relationship method. An extremely small line width of 0.014 G was measured in the ESR spectrum of deuterated 2,5-dimethoxy-1,4-benzoquinone.

The transformation of aromatic molecules into the subspace of their double bonds

A model of new submolecules is presented. As an application some absorptions of aromatic radicals are interpreted in UV and visible spectra. Extension of the model to biological systems is prejudged.

Theoretical nuclear spin-spin coupling constants using atom-atom polarizabilities.13CH and HH′ coupling constants of some [2.2.1] bicyclic compounds using the INDO approximation

Radical cations of vitamin E

Radical cations of vitamin E compounds (α-, β-, γ- and δ-tocopherols and α-, β-, γ- and δ-tocotrienols) were for the first time successfully prepared in different solvents. Their unpaired electron distribution was solved by means of EPR and ENDOR spectroscopy and assignment of isotropic hyperfine couplings was performed. The isotropic hyperfine coupling constants calculated theoretically (UB3LYP) were comparable to those studied experimentally. Radical cations were observed to exist as an intermediate product in the formation of the neutral radical. Moreover, loosening the proton from the radical cation of α-tocopherol and from α-tocotrienol produced the neutral radical, which was detected …

Micellization and Micellar Structure of a Poly(ethylene oxide)/Poly(propylene oxide)/Poly(ethylene oxide) Triblock Copolymer in Water Solution, As Studied by the Spin Probe Technique

The micellization of the triblock copolymer Pluronic P85 (poly(oxyethylene)27/poly(oxypropylene)39/poly(oxyethylene)27) in aqueous solution was followed vs temperature and addition of aliphatic alcohols, using the spin probe technique. Different types of probes properly chosen (spin-labeled (SL) poly(oxyethylene(4))nonylphenol, SL-Pluronic L62, TEMPO-laurate, TEMPO-hexanoate, CAT 4, CAT 8, CAT 11, CAT 16, and 5-, 7-, 10-, and 12-doxylstearic acids) provided information about the micellar structure (polarity, viscosity, and order degree) at different radial locations. Micellization was found to be low at room temperature, even for 10% aqueous solutions, but strongly increasing with temperatu…

Micropolarity and Order in the Reverse Micelles of L62 and L64 Pluronic Copolymers, As Studied by Molecular Probe Techniques

The reverse micelles of triblock copolymers poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) EO6PO36EO6 (Pluronic L62) and EO13PO30EO13 (Pluronic L64) in ternary (copolymer/o-xylene/water) and binary (copolymer/water) systems with different water contents were evidenced and investigated by fluorescence, absorption, and spin probe techniques. The spectral parameters of the polarity sensitive probes, 1-anilinonaphthalene-8-sulfonic acid (ANS), dansylhexadecylamine (Dansyl), pyrenesulfonic acid (PSA), 4-nitropyridine N-oxide (NP) and 4-(N,N‘-dimethyl-N-alkyl)ammonium 2,2‘,6,6‘-tetramethylpiperidine-1-oxyl iodide (CAT n), were related to the local hydration and polari…

ENDOR Spectroscopic and Molecular Orbital Study of the Dynamical Properties of the Side Chain in Radical Anions of Ubiquinones Q-1, Q-2, Q-6, and Q-10

Abstract The dynamics of the side chain of the radical anions of ubiquinones Q-1 (2,3-dimethoxy-5-methyl-6-[3-methyl-2-butenyl]-1,4-benzoquinone), Q-2, Q-6, and Q-10 have been investigated using electron nuclear double-resonance (ENDOR) spectroscopy. When radicals are produced in the liquid phase, secondary radicals are also formed. The EPR spectra of these additional radicals overlap with the radical of interest. ENDOR spectroscopy was found to be capable for studying the dynamical properties of such conditions. The temperature dependence of the isotropic hyperfine coupling constants of the β- and γ-protons of the side chain was measured. The activation energy of the rotation and other dyn…

Two-Photon Transitions in CW-ENDOR Spectra of Radicals in Fluid Solution

The radical anion of duroquinone (2,3,5,6-tetramethyl-1,4-benzoquinone) was used as a model compound to describe the low-frequency (LF) ENDOR lines observed in many radical systems. These LF lines ...

EPR, ENDOR and TRIPLE Resonance and MO Studies on Ubiquinones (Q-n): Comparison of Radical Anions and Cations of Coenzymes Q-10 and Q-6 with the Model Compounds Q-2 and Q-0.

Radical anions and cations of the biologically important coenzymes Q-6 and Q-10, which have 6 and 10 unsaturated isoprene units in their side chains, respectively, have been generated in various solvents, and the results compared with those obtained for Q-0, a ubiquinone with no isoprene units, and for decylubiquinone Q-2 which has a saturated side chain. Hyperfine splitting constants (hfsc) of methyl and methoxy protons of the substituents in the quinone ring, and beta and gamma protons of the side chain were measured by EPR and ENDOR spectroscopy for both the radical anions and cations of Q-0, Q-6 and Q-10, and for the radical anion of Q-2. The relative signs of the hfsc were determined b…

EPR and Multiple Electron Resonance Spectroscopic Indication ofpara-Nitration of Aminyl Radicals

Endor Determined Structure and Conformation of Spin-Labeled Methyl L-Phenylalanate in Frozen Solutions

The conformation of L-phenylalanine and methyl L-phenylalanate acylated at the amino nitrogen position with the nitroxyl spin-label 2,2,5,5-tetramethyl- l-oxypyrroline-3-carboxylic acid has been determined by ENDOR spectroscopy and computer based molecular modeling. ENDOR spectra of spin-labeled L- phenylalanine and the corresponding methyl ester of L-phenylalanine and of their 8-fluoro and £-fluoro derivatives in perdeuterated methanol or chloroform/toluene exhibited well resolved resonance absorptions from protons and fluorines of the amino acid moiety. From the analysis of the dependence of the ENDOR spectra on Hq, we have identified principal hyperfine coupling (hfc) components of each …