Search for highly resolved electron spin resonance spectra of the transient radical in radical polymerization

The detection of highly resolved spectra in electron spin resonance (ESR) measurements of radical polymerization is presented. Well‐resolved ESR spectra of the propagating radical were detected in the radical polymerization of several vinyl monomers with a specially designed cavity and cell. More highly resolved ESR spectra of the propagating radicals of vinyl and diene compounds were observed with aconventional spectrometer without the specially designed cavity and cell. On the basis of the ESR spectra, propagation rate constants and dynamic behavior of propagating radicals are discussed. Moreover, the application of time‐resolved ESR spectroscopy to research on the initiation process in radical polymerization is shown. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 269–285, 2002     

The resonance Raman spectrum of the aniline radical cation

The time-resolved resonance Raman spectrum of the aniline radical cation has been observed using pulse radiolysis methods. This radical exhibits a large inverse secondary isotope effect on deuteration of the NH₂ group on the CN stretching frequency. Various spectral features indicate that this radical is structurally similar to the phenoxyl radical.     

Electron spin resonance spectrum of the diphenylcyclobutene anion radical

The anion radical of 1,2-diphenylcyclobutene was studied by electron spin resonance. The hyperfine splittings were found to be 0·47 and 0·74 G for the meta-positions, 2·23 and 2·69 G for the ortho-positions and 4·21 G for the para-positions of the phenyl rings. The methylene proton splittings were 4·27 G, which would imply that the value of Q is 27 G, much lower than that of other cyclobutene anions. It was also estimated that the angle between the axis of the p-orbitals of the ethylene group and that of the phenyl group is about 30°, in agreement with that found for the tetraphenylethylene anion.     

Structures and cis-to-trans photoisomerization of hexafluoro-1,3-butadiene radical cation: electron spin resonance and computational studies

The s-cis and s-trans isomer radical cations of hexafluoro-1,3-butadiene (s-cis-HFBD+ and s-trans-HFBD+) were generated by a gamma-irradiated solid solution of the neutral HFBD molecule in solid matrix at 77 K and observed by means of electron spin resonance (ESR) and electronic spectroscopies. In comparing the experimental isotropic and anisotropic 19F hyperfine splittings with the computational ones by the DFT B3LYP and MP2 methods, the generated s-cis-HFBD+ and s-trans-HFBD+ radical cations were confirmed to be 2A2 and 2Bg electronic ground states in C2v and C2h symmetries, respectively. The present spectroscopic study revealed that the relative abundance of s-cis-HFBD+ to s-trans-HFBD+ was 4.0 immediately after being formed by gamma-irradiation, and subsequently most s-cis-HFBD+ was isomerized to s-trans-HFBD+ by visible-light illumination with 500-600 nm wavelength. The process of nonplanar HFBD ionizing to form stable planar s-cis- and s-trans-HFBD+ and the reaction mechanism of the cis-to-trans photoisomerization were discussed by (MS-)CASPT2//CASSCF calculated vertical excitation energies (Tv) and torsional potential energy curves (TPECs) of HFBD and HFBD+.     

Analysis of electron spin resonance spectra of irradiated gingers: Organic radical components derived from carbohydrates

Electron spin resonance (ESR) spectral characterizations of gingers irradiated with electron beam were studied. Complex asymmetrical spectra (near g=2.005) with major spectral components (line width=2.4 mT) and minor signals (at 6 mT apart) were observed in irradiated gingers. The spectral intensity decreased considerably 30 days after irradiation, and continued to decrease steadily thereafter. The spectra simulated on the basis of characteristics of free radical components derived from carbohydrates in gingers are in good agreement with the observed spectra. Analysis showed that shortly after irradiation the major radical components of gingers were composed of radical species derived from amylose and cellulose, and the amylose radicals subsequently decreased considerably. At 30 days after irradiation, the major radical components of gingers were composed of radical species derived from cellulose, glucose, fructose or sucrose.     

The electron spin resonance spectrum of the triphenylsilyl radical formed by the X-irradiation of monocrystalline triphenylsilane

The electron spin resonance spectrum of X-irradiated monocrystalline triphenylsilane has been studied at room temperature. The main radical species present is the triphenylsilyl radical, formed both as isolated radicals and pair-wise trapped radicals. For the radical pairs the analysis of the dipole coupling tensor indicates an inter-radical distance of 7.36 Å. The ²⁹Si hyperfine tensor has been determined, and the values discussed in terms of the electronic structure of the triphenylsilyl radical.     

L-tryptophan radical cation electron spin resonance studies: connecting solution-derived hyperfine coupling constants with protein spectral interpretations

Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce (4+) in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-Tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' beta-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron-nuclear double resonance, or high-field ESR. This approach also produces geometric parameters (dihedral angles for the beta-methylene hydrogens) that should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals.     

三苯基硅自由基的电子自旋共振研究

有机硅自由基的电子自旋共振(ESR)的研究一直十分活跃,Bock等已做了大量工作。然而,对于三苯基硅自由基的ESR研究报道却甚少。采用X射线辐照单晶生成的三苯基硅自由基的ESR谱并未获得理想的超精细结构谱,而采用三苯基硅烷与二苯甲酮热反应仅获得Ph_2COSiPh_3自由基的ESR谱。本文报道在氯仿溶液中,用无水三氯化铝与三苯基硅醇或三苯基硅烷在室温下反应,获得三苯基硅烷正离子自由基(Ph_3Si~+)ESR的研究结果,并进行计算机模拟。     

Flow injection analysis of DPPH radical based on electron spin resonance

In order to construct a rapid and selective determination system of free radicals, we developed an FIA system using an electron spin resonance (ESR) spectrophotometer (flow injection spin analysis) equipped with a flow-through flat cell. In the present investigation, 1,1-diphenyl-2-picrylhydrazyl (DPPH) was used as a model free radical. Using a single line flow system, 0.5 mM DPPH was repetitively injected. When the magnetic field was fixed at 335.3 mT, the largest change in the ESR signal was observed and obtained peak height was proportional to the concentration of DPPH radical. A double line flow system was constructed in which a carrier stream containing 0.15 mM DPPH was fed into the flat cell after confluence with a sample stream. When ascorbic acid was injected as a typical DPPH radical scavenger, a negative peak appeared in proportional to the concentration. Lower detection limit of ascorbic acid was 0.01 mM (S/N=4), sampling frequency was 13 samples per h, and a satisfactory reproducibility (CV=3.2%, 0.1 mM, n=5) was obtained. The present system was also applied to estimate the DPPH radical-scavenging activity of other substances and food samples.     

A new Lanczos-based algorithm for simulating high-frequency two-dimensional electron spin resonance spectra

The Lanczos algorithm (LA) is a useful iterative method for the reduction of a large matrix to tridiagonal form. It is a storage efficient procedure requiring only the preceding two Lanczos vectors to compute the next. The quasi-minimal residual (QMR) method is a powerful method for the solution of linear equation systems, Ax = b. In this report we provide another application of the QMR method: we incorporate QMR into the LA to monitor the convergence of the Lanczos projections in the reduction of large sparse matrices. We demonstrate that the combined approach of the LA and QMR can be utilized efficiently for the orthogonal transformation of large, but sparse, complex, symmetric matrices, such as are encountered in the simulation of slow-motional 1D- and 2D-electron spin resonance (ESR) spectra. Especially in the 2D-ESR simulations, it is essential that we store all of the Lanczos vectors obtained in the course of the LA recursions and maintain their orthogonality. In the LA-QMR application, the QMR weight matrix mitigates the problem that the Lanczos vectors lose orthogonality after many LA projections. This enables substantially more Lanczos projections, as required to achieve convergence for the more challenging ESR simulations. It, therefore, provides better accuracy for the eigenvectors and the eigenvalues of the large sparse matrices originating in 2D-ESR simulations than does the previously employed method, which is a combined approach of the LA and the conjugate-gradient (CG) methods, as evidenced by the quality and convergence of the 2D-ESR simulations. Our results show that very slow-motional 2D-ESR spectra at W-band (95 GHz) can be reliably simulated using the LA-QMR method, whereas the LA-CG consistently fails. The improvements due to the LA-QMR are of critical importance in enabling the simulation of high-frequency 2D-ESR spectra, which are characterized by their very high resolution to molecular orientation.     

The electron spin resonance spectrum of the lithium trimer in hydrocarbon matrices

The lithium metal trimer, Li₃, has been prepared in adamantane using a rotating cryostat and its electron spin resonance spectrum recorded from 4 to 298 K. It has three magnetically equivalent Li nuclei with parameters a₇(3) = 33.1 G and g = 2.001. Consequently a change of matrix from argon to adamantane has no effect on the spin distribution and structure of Li₃ which appears to be a pseudorotating dynamic Jahn-Teller molecule at all temperatures. In adamantane it is stable for several hours even at room temperature.     

Time resolved electron spin resonance of spin correlated micelle confined radical pairs: shape of the anti-phase structure

A new approach to the theory of the EPR of spin correlated radical pairs (SCRP) is formulated. It is based on spectral exchange methods as applied to the two-site model and takes into account explicitly both the motion of one quantum (transverse magnetization) and two quantum coherences (polarizations) of SCRPs. This innovation allows for the interpretation of anti phase structure (APS) spectral shape asymmetry and for the transformation of the initially created ST0RPM polarization into the APS spectral pattern. The results of this method as applied to micellized spin correlated radical pairs have been compared with the exact numerical solution of the corresponding stochastic Liouville equation and is commented on.     

Combination of neural networks and DFT calculations for the comprehensive analysis of FDMPO radical adducts from fast isotropic electron spin resonance spectra

The 4-hydroxy-5,5-dimethyl-2-trifluoromethylpyrroline-1-oxide (FDMPO) spin trap is very attractive for spin trapping studies due to its high stability and high reaction rates with various free radicals. However, the identification of FDMPO radical adducts is a challenging task since they have very comparable Electron Spin Resonance (ESR) spectra. Here we propose a new method for the analysis and interpretation of the ESR spectra of FDMPO radical adducts. Thus, overlapping ESR spectra were analyzed using computer simulations. As a result, the N- and F-hyperfine splitting constants were obtained. Furthermore, an artificial neural network (ANN) was adopted to identify radical adducts formed during various processes (e.g., Fenton reaction, cleavage of peracetic acid over MnO(2), etc.). The ANN was effective on both "known" FDMPO radical adducts measured in slightly different solvents and not a priori "known" FDMPO radical adducts. Finally, the N- and F-hyperfine splitting constants of ·OH, ·CH(3), ·CH(2)OH, and CH(3)(C═O)O(·) radical adducts of FDMPO were calculated using density functional theory (DFT) at the B3LYP/6-31G(d,p)//B3LYP/6-31G++//B3LYP/EPR-II level of theory to confirm the experimental data.     

Structures of the hexafluorocyclopropane, octafluorocyclobutane, and decafluorocyclopentane radical anions probed by experimental and computational studies of anisotropic electron spin resonance (ESR) spectra

Anisotropic electron spin resonance (ESR) spectra are reported for the radical anions of hexafluorocyclopropane (c-C(3)F(6)(-)), octafluorocyclobutane (c-C(4)F(8)(-)), and decafluorocyclopentane (c-C(5)F(10)(-)) generated via gamma-irradiation in plastically crystalline tetramethylsilane (TMS) and rigid 2-methyltetrahydrofuran (MTHF) matrices. By combining the analysis of these experimental ESR spectra involving anisotropic hyperfine (hf) couplings with a series of quantum chemical computations, the geometrical and electronic structure of these unusual perfluorocycloalkane radical anions have been characterized more fully than in previous studies that considered only the isotropic couplings. Unrestricted Hartree-Fock (UHF) computations with the 6-311+G(d,p) basis set predict planar ring structures for all three radical anions, the ground electronic states being (2)A(2)(") for c-C(3)F(6)(-) (D(3h) symmetry), (2)A(2u) for c-C(4)F(8)(-) (D(4h)), and (2)A(2)(") for c-C(5)F(10)(-) (D(5h)), in which the respective six, eight, and ten 19F-atoms are equivalent by symmetry. A successful test of the theoretical computation is indicated by the fact that the isotropic 19F hf couplings computed by the B3LYP method with the 6-311+G(2df,p) basis set for the optimized geometries are in almost perfect agreement with the experimental values: viz., 19.8 mT (exp) vs 19.78 mT (calc) for c-C(3)F(6)(-); 14.85 mT (exp) vs 14.84 mT (calc) for c-C(4)F(8)(-); 11.6 mT (exp) vs 11.65 mT (calc) for c-C(5)F(10)(-). Consequently, the same computation method has been applied to calculate the almost axially symmetric anisotropic 19F hf couplings for the magnetically equivalent 19F atoms: (-4.90 mT, -4.84 mT, 9.75 mT) for c-C(3)F(6), (-3.54 mT, -3.48 mT, 7.02 mT) for c-C(4)F(8)(-), and (-2.62 mT, -2.56 mT, 5.18 mT) for c-C(5)F(10)(-). ESR spectral simulations performed using the computed principal values of the hf couplings and the spatial orientations of the 19F nuclei as input parameters reveal an excellent fit to the experimental anisotropic ESR spectra of c-C(3)F(6)(-), c-C(4)F(8)(-), and c-C(5)F(10)(-), thereby providing a convincing proof of the highly symmetric D(nh) structures that are predicted for these negative ions. Furthermore, using the computed 19F principal values and their orientations, the effective 19F anisotropic hf couplings along the molecular symmetry axes were evaluated for c-C(3)F(6)(-) and c-C(4)F(8)(-) and successfully correlated with the positions of the characteristic outermost features in both the experimental and calculated anisotropic spectra. In addition, the electronic excitation energies and oscillator strengths for the c-C(3)F(6)(-) , c-C(4)F(8)(-), and c-C(5)F(10)(-) radical anions were computed for the first time using time-dependent density functional theory (TD-DFT) methods.     

Electron spin resonance spectrum of a 5-membered cyclic alkoxy nitroxyl radical

The esr spectrum of a 5-membered cyclic alkoxy nitroxyl radical is reported. 20111979     

Simulating electron spin resonance spectra of nitroxide spin labels from molecular dynamics and stochastic trajectories

Simulating electron spin resonance spectra of nitroxide spin labels from motional models is necessary for the quantitative analysis of experimental spectra. We present a framework for modeling the spin label dynamics by using trajectories such as those from molecular dynamics (MD) simulations combined with stochastic treatment of the global protein tumbling. This is achieved in the time domain after two efficient numerical integrators are developed: One for the quantal dynamics of the spins and the other for the classical rotational diffusion. For the quantal dynamics, we propagate the relevant part of the spin density matrix in Hilbert space. For the diffusional tumbling, we work with quaternions, which enables the treatment of anisotropic diffusion in a potential expanded as a sum of spherical harmonics. Time-averaging arguments are invoked to bridge the gap between the smaller time step of the MD trajectories and the larger time steps appropriate for the rotational diffusion and/or quantal spin dynamics.     

The electron spin polarized (CIDEP) spectrum of the propan-2-olyl radical

It is demonstrated that the origin of the absorptive contribution observed in the spin polarized esr spectrum of the propan-2-olyl radical when it is created by flash-photolysis of propan-2-one (acetone) in a hydrogen-donating solvent is not the triplet mechanism of CIDEP, as previously assumed. It is shown to arise not in the photochemistry or photophysics of the parent molecule, but rather to be a property of the radical pair itself. Arguments are presented to demonstrate that its origins may lie in an unidentified novel polarization process, rather than the possible redistribution of level populations via very fast relaxation processes.