Studies on coherent and incoherent spin dynamics that control the magnetic field effect on photogenerated radical pairs

Since 1970s, magnetic field effects (MFEs) on photogenerated radical pairs have been the centre of focus in the field of spin chemistry. The MFE attributes to quantum mechanical interconversion between the singlet and triplet radical pair states and subsequent spin-selective recombination reactions. In this New View article, the author picks up two hot topics studied during the last two decades, which are (i) so-called low field effect (LFE) and (ii) 2J-resonance MFE on fixed distance donor–acceptor linked molecules. In both of the topics, quantum mechanical explanations are given referring to recent reports, and some novel calculations have been carried out for bridging theoretical and experimental data for long-lived radical pairs. For the first topic, time domain calculations of coherent state mixing have been carried out for elucidation of hyperfine (HF) structure dependence of the LFE. For the second topic, Monte Carlo simulations of the torsional motion of polyaromatic linker unit have been carried out for the demonstration of fast decoherence in such rigid molecules. From these considerations, future possibilities of MFE studies on photo-functional materials and biomolecules have been indicated.     

13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?

Metal–organic frameworks (MOFs) are a class of important porous materials with many current and potential applications. Their applications almost always involve the interaction between host framework and guest species. Therefore, understanding of host–guest interaction in MOF systems is fundamentally important. Solid-state NMR spectroscopy is an excellent technique for investigating host–guest interaction as it provides information complementary to that obtained from X-ray diffraction. In this work, using MOF α-Mg₃(HCOO)₆ as an example, we demonstrated that ¹³C chemical shift tensor of organic linker can be utilized to probe the host–guest interaction in MOFs. Obtaining ¹³C chemical shift tensor components (δ₁₁, δ₂₂, and δ₃₃, where δ₁₁ ≥ δ₂₂ ≥ δ₃₃) in this MOF is particularly challenging as there are six coordinatively equivalent but crystallographically non-equivalent carbons in the unit cell with very similar local coordination environment. Two-dimensional magic-angle-turning experiments were employed to measure the ¹³C chemical shift tensors of each individual crystallographically non-equivalent carbon in three microporous α-Mg₃(HCOO)₆ samples with different guest species. The results indicate that the δ₂₂ component (with its direction approximately being co-planar with the formate anion and perpendicular to the C−H bond) is more sensitive to the adsorbate molecules inside the MOF channel due to the weak C−H···O hydrogen bonding or the ring current effect of benzene. The ¹³C isotropic chemical shift, on the other hand, seems much less sensitive to the subtle changes in the local environment around formate linker induced by adsorption. The approach described in this study may be used in future studies on host–guest interaction within MOFs.     

Electrochemical sensor based on super-magnetic metal–organic framework@molecularly imprinted polymer for Sarcosine detection in urine

Accurate determination of Sarcosine (SAR) in urine with high sensitivity and selectivity is important, because it was recently recommended as a prospective biomarker for prostate cancer (PCa) and significant for the early identification of PCa. In this study, an electrochemical sensor based on Fe₃O₄ incorporated metal–organic frameworks (MOFs) @molecularly imprinted polymer (MIP) was constructed for SAR detection. Magnetic Fe₃O₄ nanoparticles embedded zeolitic imidazolate framework-8 (ZIF-8) was used as the support of MIP. MIP provides specific recognition sites for template molecules SAR and MOFs increase the rate of mass transfer and adsorption capacity due to the porous structure. The synthesized super-magnetic Fe₃O₄@ZIF-8@MIP was self-assembled onto an Au electrode in magnetic field and used as the sensing unit of electrochemical sensor. Cyclic voltammetry was used to monitor the electrochemical behavior, and the binding of SAR resulted in a reduction in the measured current. The results revealed a wide linear range from 1 to 100 pM towards trace SAR determination, with extremely low limit of detection down to 0.4 pM. In conclusion, the Fe₃O₄@ZIF-8@MIP based sensor provides a selective, sensitive, and convenient method for SAR diagnosis and other cancer marker detection.     

Nanoscale detection of faint machinery vibration using the NV center in diamond

We propose a novel method for detection of the faint machinery vibration at the nanometer resolution based on the spin magnetic resonant effect. A suspension magnet acts as a vibration sensor to transfer the vibration signals as the magnetic field fluctuation to excite the spin magnetic resonance. Due to the high sensitivity of the magnetic field of the nitrogen-vacancy center in diamond, the theoretical detection limit of mechanical vibration is as high as 5.7 nm, and the actual measurement resolution reached 12.8 nm, and proved the potential for further improvement to ∼pm resolution. The feasibility of this method is verified by dynamic tests. This method provides a novel approach for the detection of micro-mechanical vibrations.     

Finite-time singularity formation at a magnetic neutral line in Hall magnetohydrodynamics

The formation of a current sheet in a weakly collisional plasma can be modelled as a finite-time singularity solution of magnetohydrodynamic equations. We use an exact self-similar solution to confirm and generalise a previous finding that, in sharp contrast to two-dimensional solutions in standard MHD, a finite-time collapse to a current sheet can occur in Hall MHD. We derive a criterion for the finite-time singularity in terms of initial conditions, and we use an intermediate asymptotic solution for the evolution of an axial magnetic field to obtain a general expression for the singularity formation time. We illustrate the analytical results by numerical solutions.     

Ab initio and Monte Carlo studies of phase transitions and magnetic properties of YCrO3: Heisenberg model

By using the density functional theory (DFT) and Monte Carlo simulations (MCS) with the Heisenberg model, we have studied magnetic properties of the bulk perovskite YCrO₃. The exchange couplings of the Heisenberg model and the magnetic anisotropy are investigated. The 110 direction in the crystalline structure of the compound has shown the minimum energy, it is the easy magnetic direction. Using Monte Carlo simulations, the magnetizations behavior, the effects of system parameters and the critical exponents of the compound YCrO₃ are implemented. It is shown that the bulk perovskite YCrO₃ belongs to the 3D Heisenberg universality class.     

Radial breathing-mode frequency of elastically confined spherical nanoparticles subjected to circumferential magnetic field

Knowledge of the vibrational properties of nanoparticles is of fundamental interest since it is a signature of their morphology, and it can be utilized to characterize their physical properties. In addition, the vibration characteristics of the nanoparticles coupled with surrounding media and subjected to magnetic field are of recent interest. This paper develops an analytical approach to study the radial breathing-mode frequency of elastically confined spherical nanoparticles subjected to magnetic field. Based on Maxwell's equations, the nonlocal differential equation of radial motion is derived in terms of radial displacement and Lorentz's force. Bessel functions are used to obtain a frequency equation. The model is justified by a good agreement between the results given by the present model and available experimental and atomic simulation data. Furthermore, the model is used to elucidate the effect of nanoparticle size, the magnetic field and the stiffness of the elastic medium on the radial breathing-mode frequencies of several nanoparticles. Our results reveal that the effects of the magnetic field and the elastic medium are significant for nanoparticle with small size.