CIDEP Created by the Quenching of Photo-Excited Tryptophan at Protein Surface: A Challenge to CIDEP Probing of Protein Structural Changes

Quenching of the triplet excited state of molecular tryptophan by nitroxide radical in 1,4-dioxane and water solutions was investigated by means of time-resolved electron paramagnetic resonance (EPR) and Fourier-transform (FT)-EPR. The chemically induced dynamic electron polarization (CIDEP) signals with net emissive phase were recorded at these quenching events and were analyzed through radical-triplet pair mechanism. The CIDEP time profiles were well reproduced by Bloch and kinetic equations, assuming radical-triplet pair mechanism with the appropriate quenching rate constants. From a comparison of the simulation and the experiment, CIDEP enhancement factor in 1,4-dioxane was determined to be −30 × P _eq, where P _eq is the spin polarization of nitroxide at thermal equilibrium. Net emissive CIDEP was also observed by FT-EPR measurements on the nitroxide quenching of the triplet excited state of tryptophan residue in α-lactalbumin. Magnitude of CIDEP created in α-lactalbumin/nitroxide system depends on the pH condition of α-lactalbumin solution, which is related to protein folding dynamics. We argue the CIDEP mechanism at the α-lactalbumin surface and propose a possibility of a novel CIDEP method to probe a protein surface and structural changes.     

Eigenstate expansions in a soluble model of identical particle scattering

Solutions to the Schrödinger equation and the inhomogeneous equation for the case of two identical particles interacting with a center of force are studied. Eigenstate expansions for solving each equation are explicitly introduced and their properties discussed. The case when the interparticle interaction v₁₂ is zero is then examined; this is a completely soluble problem. The eigenstate expansion solutions for the Schrödinger and inhomogeneous equations are used to explore the means by which the correct solution is obtained. Finally, approximate solutions, obtained by truncating the eigenfunction expansions, are introduced. It is seen that both methods lead to the correct amplitude when τ₁₂ = 0, even though the approximate solution to the inhomogeneous equation does not lead, in the end, to an antisymmetric solution.     

A Chemically Induced Magnetic Polarization Study of the Photoreduction of Tetrachloro-p-Benzoquinone

The potential applications of chemically induced dynamic magnetic polarization in photochemistry have recently been emphasized^1. The better understanding of the mechanisms involved in the magnetic polarization permits the combination of CIDEP, CIDNP, and the conventional e.s.r. and n.m.r. techniques to be a powerful tool with which to study organic photochemistry involving excited triplet states and free radical reactions. The recent discovery of electron polarization in photosynthesis systems² is expected to open another exciting area for magnetic polarization applications. The photolysis of tetrachloro-p-benzoquinone, p-Chloranil, has attracted much attention^3,4 as model system in conventional e.s.r. studies. We report here a further investigation of the photoreduction of p-chloranil by a variety of hydrogen donors using the combined e.s.r., CIDEP and CIDNP method.     

吩噻嗪-1,4萘醌-乙二醇体系光化学过程的时间分辨ESR研究

用时间分辨ＥＳＲ方法研究了吩噻嗪（ＰＴＨ）－１，４－萘醌（ＮＱ）－乙二醇（ＲＨ）体系中的光化学过程．只观察到萘醌的中性半醌自由基ＮＱＨ．＊的全发射极化的ＣＩＤＥＰ（化学诱导动态极化）信号，并未观察到极化的萘醌负离子ＮＱ－·＊的ＣＩＤＥＰ信号，表明ＲＨ与三重态ＮＱ间的质子转移反应远比ＰＴＨ与ＮＱ间的电子转移反应为快．ＮＱＨ．＊的ＣＩＤＥＰ信号随ｐＨ值的变化表明体系中同时有极化自由基ＮＱＨ．＊与ＮＱＨ．＋＊２存在，并且其间有质子交换．     

吩噻嗪-1,4萘醌-乙二醇体系光化学过程的时间分辨ESR研究

用时间分辨ESR方法研究了吩噻嗪(PTH)-1,4-萘醌(NQ)-乙二醇(RH)体系中的光化学过程.只观察到萘醌的中性半醌自由基NQH^*的全发射极化的CIDEP(化学诱导动态极化)信号,并未观察到极化的萘醌负离子NQ·^-*的CIDEP信号,表明RH与三重态NQ间的质子转移反应远比PTH与NQ间的电子转移反应为快.NQH·^*的CIDEP信号随pH值的变化表明体系中同时有极化自由基NQH·^*与NQH·₂^+*存在,并且其间有质子交换.     

On the relation of Regge-trajectories to degenerate classical solutions of equations of motion

The relation of orbital excitations E = E(l) to critical curves in the initial data (l, E)-plane of classical equations of motions is pointed out. In addition it is shown that the string motion with the linear trajectory J=α′m² corresponds to a degenerate solution of the inhomogeneous Maxwell equations.     

激光引发自由基反应磁效应的光谱学研究

“动态自旋化学”(dynamic spin chemistry)作为一门新兴的交叉研究领域,其重要性已得到广泛的共识。涉及的研究内容包括： 化学反应的磁效应(MFE)、同位素效应(MIE)、化学诱导动态核极化(CIDNP)和化学诱导动态电子极化(CIDEP)。文章简要介绍了激光引发自由基反应的磁效应发展历史及其光谱学研究方法。分析并总结了自由基反应磁效应产生的原因、单-三转换理论及磁效应机理。同时,也为国内同行介绍了自由基反应磁效应研究新的发展动态。     

Unitarity and the inhomogeneous equations method for identical particle scattering

A K-matrix solution to the coupled, inhomogeneous equations describing the scattering of a particle by a system of identical particles is developed. It is shown that K is a sum of two terms, one arising from the homogeneous solution and one from the particular integral. The former is a direct contribution, i.e., with no exchange, while the latter is a pure exchange contribution. Thus, as in the previously studied case of the T matrix arising from this system of equations, the direct and exchange portions of K are additive, and can be computed separately. A unitary S matrix is obtained from K in the usual way: S = (1 + iK)(1 − iK)⁻¹. The problem of how to calculate K when an apparent two-channel problem is actually a two-particle problem with the channels referring to the identical particle labels is also solved.     

FT-EPR study of alkyl radicals formed in the photochemical reaction of Re(alkyl)(α-diimine) and Ru(alkyl)(α-diimine) complexes

A Fourier transform EPR (FT-EPR) study was made of the photochemistry of [Re(R)(CO)₃ (α-diimine)] and [Ru(E)(R)(CO)₂(α-diimine)] complexes, where R = alkyl or benzyl, E = I or SnPh₃, and α-diimine = 4,4′-dimethyl-2,2′-bipyridine (DMB) orN,N′-diisopropyl-1,4-diazabutadiene (iPr-DAB). Photoexcitation of these complexes leads to homolysis of the metal-alkyl (benzyl) bonds as evident from the detection of the spectra of the alkyl (benzyl) radicals. FT-EPR spectra display strong spin polarization effects attributed to Triplet Mechanism (TM) and Radical Pair Mechanism (RPM) Chemically Induced Dynamic Electron Polarization (CIDEP). CIDEP patterns point to bond dissociation via a triplet state precursor. For a number of complexes, spin polarization was found to exhibit unusually large solvent effects, whereas for one complex the CIDEP pattern proved to be sensitive to the wavelength of laser light used to initiate bond dissociation. These effects reflect the strong dependence of CIDEP on the character of the excited states involved in the photochemical reactions and contribute to the understanding of the reaction mechanism.     

Photo-Induced Electron Transfer in P3DDT, P3OT, M3EH-PPV Conjugated Polymers Blended with Maleic Anhydride in THF Solution Under UV Flash Photolysis Studied by Means of CW TR ESR

Free-radical signals of positive polarons in conjugated polymer chains and maleic anhydride (MA) anion radicals were registered in poly(3-octylthiophene) P3OT:MA and (poly[2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5-(2-ethylhexyloxy)?C(1,4-phenylene-1,2-ethenylene)]) M3EH-PPV:MA blends in tetrahydrofuran (THF) solutions under ultraviolet flash photolysis (308?nm) by continuous-wave time-resolved electron spin resonance. Their emissive chemically induced dynamic electron polarization (CIDEP) originated mainly from excited triplet states (triplet mechanism of CIDEP) and partly by from the radical pair mechanism due to the singlet?Ctriplet mixing states. The observed M3EH-PPV polaron spectrum (g ₀?=?2.0029) supports the supposition that the previously registered CIDEP spectra in P3DDT:MA blends (g ₀?=?2.0021) can be attributed to the polaron signals instead of the possible solvate electron signal one.     

Multi-leg integrable ladder models

We construct integrable spin chains with inhomogeneous periodic disposition of the anisotropy parameter. The periodicity holds for both auxiliary (space) and quantum (time) directions. The integrability of the model is based on a set of coupled Yang–Baxter equations. This construction yields P-leg integrable ladder Hamiltonians. We analyse the corresponding quantum group symmetry and present algebraic Bethe ansatz (ABA) solution.     

Photooxidation of Histidine by 3,3′,4,4′-Benzophenone Tetracarboxylic Acid in Aqueous Solution: Time-Resolved and Field-Dependent CIDNP Study

The photooxidation reaction between 3,3′,4,4′-benzophenone tetracarboxylic acid (TCBP) and l-histidine (His) has been investigated in neutral aqueous solution using the technique of chemically induced dynamic nuclear polarization (CIDNP). Relative values of ¹³C isotropic hyperfine couplings in the TCBP and His radicals were obtained from the ¹³C-time-resolved CIDNP spectrum, recorded during the photoreaction of TCBP with His at natural abundance of the magnetic isotope ¹³C. Good agreement was found for the hyperfine coupling constants of the TCBP ketyl radical calculated using methods of density functional theory, and those obtained from the ¹³C-time-resolved CIDNP spectrum. The mechanism of the quenching reaction of triplet-excited TCBP by His in neutral aqueous solution was established. ¹H CIDNP field dependencies for the photoreaction of TCBP with His were obtained and the g-factor of the histidyl radical was found.     

Multiplet-to-net CIDEP conversion by MW-pulses with adiabatically ramped amplitude

ABSTRACT

A method is proposed to manipulate electron spin order of spin-correlated radical pairs. As radical pairs are often born in a well-defined spin state, e.g. in the singlet state, they acquire Chemically Induced Dynamic Electron Polarisation (CIDEP). In the case of singlet-state preparation CIDEP is of the multiplet (or anti-phase) type resulting in reduction of EPR (electron paramagnetic resonance) signals due to overlap of absorptive and emissive lines in the spectrum. Here we propose to convert the singlet spin order into net magnetisation of the radical pair by applying a microwave field, with its amplitude slowly (adiabatically) reduced to zero. We demonstrate that by properly choosing the microwave frequency one can completely convert the singlet order into net polarisation of the radical pair with significant enhancement of the signal as compared to multiplet CIDEP. Calculations show that the technique is operative for both weakly coupled and strongly coupled spin pairs. Potential applications of the method are discussed.     

High-performance modeling acoustic and elastic waves using the parallel Dichotomy Algorithm

A high-performance parallel algorithm is proposed for modeling the propagation of acoustic and elastic waves in inhomogeneous media. An initial boundary-value problem is replaced by a series of boundary-value problems for a constant elliptic operator and different right-hand sides via the integral Laguerre transform. It is proposed to solve difference equations by the conjugate gradient method for acoustic equations and by the GMRES(k) method for modeling elastic waves. A preconditioning operator was the Laplace operator that is inverted using the variable separation method. The novelty of the proposed algorithm is using the Dichotomy Algorithm [26], which was designed for solving a series of tridiagonal systems of linear equations, in the context of the preconditioning operator inversion. Via considering analytical solutions, it is shown that modeling wave processes for long instants of time requires high-resolution meshes. The proposed parallel fine-mesh algorithm enabled to solve real application seismic problems in acceptable time and with high accuracy. By solving model problems, it is demonstrated that the considered parallel algorithm possesses high performance and efficiency over a wide range of the number of processors (from 2 to 8192).     

Dynamic electron polarization created by the radical-triplet pair mechanism: Application to the studies on excited state deactivation processes by free radicals

The radical-triplet pair mechanism for chemically induced dynamic electron polarization (CIDEP) created in the quenching of excited state molecules by free radicals is explained on the basis of recent time-resolved electron spin resonance spectroscopic results and theoretical studies. The CIDEP of 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) and galvinoxyl radicals exhibit various CIDEP patterns of net and mutliplet types and CIDEP phases of absorption and emission. The CIDEP patterns are described by the quartet-doublet state mixings within the radical-triplet encounter pairs. The mixings by the spin-dipolar and the hyperfine interactions are responsible for the net and the multiplet patterns, respectively. The factors controlling the CIDEP phases are the spin multiplicity of the excited state quenched by radicals and the sign of the intermolecular exchange interaction of the radical-triplet encounter pairs. In particular, the intermolecular charge transfer effect on the exchange interaction is discussed much in detail from the viewpoints of CIDEP magnitudes and phases. A CIDEP creation in the O₂(¹Δ_g)-TEMPO system is also introduced and is described by the radical-triplet pair mechanisms. Applications of this CIDEP used as a probe of O₂(¹Δ_g) in condensed phase are mentioned.     

Spin Chemistry Investigation of Peculiarities of Photoinduced Electron Transfer in Donor–Acceptor Linked System

Photoinduced intramolecular electron transfer in linked systems, (R,S)- and (S,S)-naproxen-N-methylpyrrolidine dyads, has been studied by means of spin chemistry methods [magnetic field effect and chemically induced dynamic nuclear polarization (CIDNP)]. The relative yield of the triplet state of the dyads in different magnetic field has been measured, and dependences of the high-field CIDNP of the N-methylpyrrolidine fragment on solvent polarity have been investigated. However, both (S,S)- and (R,S)-enantiomers demonstrate almost identical CIDNP effects for the entire range of polarity. It has been demonstrated that the main peculiarities of photoprocesses in this linked system are connected with the participation of singlet exciplex alongside with photoinduced intramolecular electron transfer in chromophore excited state quenching.     

An elastodynamic solution of finite long orthotropic hollow cylinder under torsion impact

The paper presents an analytical method to solve the elastodynamic problem of a finite-length orthotropic hollow cylinder subjected to a torsion impact often occurring in engineering fields. The elastodynamic solution is composed of a quasi-static solution of homogeneous equation satisfied with the non-homogeneous boundary condition and a dynamic solution of non-homogeneous equation satisfied with homogeneous boundary condition. The quasi-static solution can be obtained by directly solving the quasi-static equation satisfied with the non-homogeneous boundary condition. The solution of a non-homogeneous dynamic equation is obtained by means of a finite Hankel transform to a radial variable r, Laplace transform to a time variable t and finite Fourier transform to an axial variable z. Thus, the elastodynamic solution of the finite length of an orthotropic hollow cylinder subjected to a torsion impact is obtained. On the other hand, a dynamic finite element for the same problem is also carried out by applying the ANSYS finite-element analysis system. Comparing the theoretical solution with finite-element solution, it can be found that two kinds of results obtained by making use of two different solving methods are suitably approached. Therefore, it is further concluded that the methods and computing processes of the theoretical solution are effective and accurate.     

On the criterion for effectiveness of wave linear transformation in a smoothly inhomogeneous medium and of nonadiabatic transitions during atomic collisions

A universal criterion for effectiveness of linear transformation of waves with locally close characteristic exponents in smoothly inhomogeneous media is obtained. The same criterion is applicable for estimating the effectiveness of nonadiabatic transitions in slow atomic collisions. The formalism developed for an analysis of the linear interaction of waves is based of the WKB asymptotic form of the solution of a scalar nth order ordinary differential equation. The obtained criterion can be applied in any practical problem for drawing a conclusion about the effectiveness of the linear interaction of modes if only the characteristic equation of waves in a homogeneous medium and the coefficients of the initial differential equation are known. In this case, the solution of the problem is reduced to elementary arithmetic calculations.