Hyperfine coupling dependence of the effects of weak magnetic fields on the recombination reactions of radicals generated from polymerisation photoinitiators

The recombination reactions of free radicals formed from the photolysis of a series of polymerisation photoinitiators were studied using time-resolved infrared spectroscopy. All molecules showed Zeeman magnetic field effects (MFEs) in the field range 0-37 mT and those molecules that produced radical pairs with average hyperfine couplings greater than 5 mT showed substantial inverted field effects at fields of less than 10 mT (so-called low field effects, LFEs). Monte Carlo simulations with full treatment of all the isotropic hyperfine couplings in the spin Hamiltonian reproduced well the observed field effects. The use of the usual analysis based on the calculated B1/2 value for the radical pair was found to be inappropriate in systems with substantial LFEs, but simple correlations between this B1/2 value and the observed field features were established.     

Dynamics of magnetic-field-induced clustering in ionic ferrofluids from Raman scattering

Using Raman spectroscopy, the authors have investigated the aggregation/disgregation of magnetic nanoparticles in dense ionic ferrofluids (IFF) into clusters due to the action of an inhomogeneous external magnetic field. Evidence for changes in particle density and/or effective cluster size were obtained from the variation of the Raman intensity in a time window from 10 s to 10 min for magnetic fields up to 350 mT and at a temperature of 28 degrees C. Clustering sets in already at very low fields (>15 mT) and the IFF samples exhibit a clear hysteresis in the Raman spectra after releasing the magnetic field, which lasts for many hours at room temperature. The authors determined the characteristic times of the two competing processes, that of field-induced cluster formation and, at room temperature, that of thermal-activated dissociation, to range from 100 to 150 s.     

Long-range jump versus stepwise hops: magnetic field effects on the charge-transfer fluorescence from photoconductive polymer films

Magnetic field effects on the charge-transfer (CT) fluorescence of a 1,2,4,5-tetracyanobenzene-doped poly(N-vinylcarbazole) thin film were investigated to clarify the primary process in photoconductive organic amorphous solid. The CT fluorescence increased with increasing magnetic field until 10 mT, and then it showed the dip around 40-50 mT. The hyperfine coupling mechanism observed in the low field and the level-crossing mechanism observed around 46 mT clearly indicate that the spin-conservative stepwise hole hops take place in the films. The boundary distance determined from the simulation based on the stepwise hopping model almost agreed with the interionic separation estimated within the Onsager analysis.     

Acute effects of whole-body exposure to static magnetic fields and 50-Hz electromagnetic fields on muscle microcirculation in anesthetized mice

Acute microhemodynamic effects of static and alternating magnetic fields at a threshold level were investigated on modulating the muscle capillary mirocirculation in pentobarbital-anesthetized mice. The skin in a tibialis anterior was circularly removed with 1.5 mm diameter for intravital-microscopic recording of the capillary blood velocity in the tibialis anterior muscle. Fluorescein isothiocyanate (FITC)-labeled dextran (MW 150 kDa) was used for an in vivo fluorescent plasma marker of the muscle capillaries. Following a bolus injection of FITC-dextran solution into the caudal vein, the peak blood velocity in the muscle capillaries was measured prior to, during, and following exposure to static magnetic fields (SMF) or 50-Hz electromagnetic fields (EMF) using a fluorescence epi-illumination system. The whole body of experimental animals, placed on the observing stage of a fluorescence microscope, was exposed to SMF (0.3, 1 and 10 mT) or 50-Hz EMF (0.3 and 1 mT) for 10 min using a specially devised electromagnet. For sham exposure, the electromagnet was not energized. During exposure and post-exposure to SMF of 10 mT, the peak blood velocity significantly increased as compared to sham exposure. After the withdrawal of SMF and 50-Hz EMF of 1 mT, significant similar effects on the blood velocity were present or enhanced. These findings suggest that field intensity of 1 mT might be considered as a threshold level for enhancing muscle microcirculation under pentobarbital-induced hypnosis.     

Electrostimulation of proliferation of the denitrifying bacterium Pseudomonas stutzeri

The electrostimulation of proliferation of the denitrification strain Pseudomonas stutzeri occurs in an anaerobic culture by a magnetic flux around 1 mT inducing a low current in the electric field fermenter wrapped by Helmholtz coils. After 10 h of treatment the biomass was higher than in the control fermenter by 10–30% depending on magnetic flux intensity.     

Interplay between crystal and magnetic structure of the anion-radical salt (N-Me-2,6-di-Me–Py)(TCNQ)2 (Py is pyridine)

Genuine organic anion-radical salt (N-Me-2,6-di-Me–Py)(TCNQ)₂ with pyridine-based cation was synthesized and its crystal structure was resolved. The DC magnetic susceptibility was measured in temperature range from 2 K to 300 K in magnetic fields 10 mT, 100 mT and 1 T. Zero field cooling (ZFC) and field cooling (FC) modes were used. The results were studied in terms of one-dimensional magnetic models and we have found that the most suitable of them is an antiferromagnetic linear Heisenberg S = 1/2 system with small amount of free spins. An additional peak observed at low temperatures can be explained by an interchain coupling between free chain-end spins.     

In Situ and Ex Situ Low‐Field NMR Spectroscopy and MRI Endowed by SABRE Hyperpolarization

By using 5.75 and 47.5 mT nuclear magnetic resonance (NMR) spectroscopy, up to 10⁵‐fold sensitivity enhancement through signal amplification by reversible exchange (SABRE) was enabled, and subsecond temporal resolution was used to monitor an exchange reaction that resulted in the buildup and decay of hyperpolarized species after parahydrogen bubbling. We demonstrated the high‐resolution low‐field proton magnetic resonance imaging (MRI) of pyridine in a 47.5 mT magnetic field endowed by SABRE. Molecular imaging (i.e. imaging of dilute hyperpolarized substances rather than the bulk medium) was conducted in two regimes: in situ real‐time MRI of the reaction mixture (in which pyridine was hyperpolarized), and ex situ MRI (in which hyperpolarization decays) of the liquid hyperpolarized product. Low‐field (milli‐Tesla range, e.g. 5.75 and 47.5 mT used in this study) parahydrogen‐enhanced NMR and MRI, which are free from the limitations of high‐field magnetic resonance (including susceptibility‐induced gradients of the static magnetic field at phase interfaces), potentially enables new imaging applications as well as differentiation of hyperpolarized chemical species on demand by exploiting spin manipulations with static and alternating magnetic fields.     

Effect of electromagnetic fields on the denitrification activity of Paracoccus denitrificans

Enzymatic activity (denitrification) of Paracoccus denitrificans was estimated electrochemically by reduction of duroquinone (DQ). Graphite electrodes covered with whole bacterial cells behind a dialysis membrane were used for measurement. P. denitrificans reduce nitrate and/or nitrite under anaerobic conditions to nitrogen gas. DQ acts as an electron mediator. After donation of the electrons to the respiratory system of the bacteria, produced DQ is reduced to durohydroquinone on the electrode surface electrocatalytically. P. denitrificans were exposed to low-frequency magnetic field (10 mT, 50 Hz) for 24 min. In comparison with the control samples, the reduction peak of I-E curves that represent denitrification activity of the cells decreased significantly after magnetic field exposure. The decrease of the peak current was about 20%. The CFU-colony forming units-method was used to estimate the number of surviving bacteria. After 24 min exposure of 10 mT magnetic field P. denitrificans culture on electrode indicates 21% bacterial death.     

RESEARCH NOTE: TRIPLET RADICAL ION PAIR STATE OF THE Zn-PORPHYRIN-VIOLOGEN DYAD AS A MAGNETIC FIELD SENSITIVE PROBE OF PHASE TRANSITIONS IN SMALL UNILAMELLAR VESICLES

The magnetic field effect on the recombination kinetics of the triplet radical ion pair state (RIPS) of the Zn-porphyrin-viologen dyad (P-Ph-Vi2+) in the small unilamellar vesicles (SUV) of D,L-dipalmitoyl-alpha-phosphatidylcholine has been studied by the nanosecond laser flash photolysis technique at 5-60 degrees C. The increase in temperature from 25 to 40 degrees C enhances the rate constant (kr) of the RIPS recombination in zero magnetic field from 0.9 x 10(6) to 1.6 x 10(6) s-1, while kr is temperature insensitive at 5-25 and 40-60 degrees C. The typical break in the kr temperature dependence is observed in the temperature range of the phase transition of the SUV bilayers from the solid to the fluid state. The kr value in a strong magnetic field (B = 0.24 T) is equal to 2.7 x 10(5) s-1 and it is independent of temperature at 5-60 degrees C. The shape of the magnetic field dependence of kr is unaffected by the phase transition of the SUV bilayers and is characterized by the existence of an initial plateau of kr at B = 0 to 0.5 mT.     

Effect of a weak magnetic field on the reaction between neutral free radicals in isotropic solution

Radical recombination following the photodissociation of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone in isotropic solution was monitored using time-resolved infrared spectroscopy. The rate of radical recombination was determined to decrease in the presence of a magnetic field of greater than 5 mT and to increase in the presence of a magnetic field smaller than 5 mT.     

Magnetic field affects enzymatic ATP synthesis

The rate of ATP synthesis by creatine kinase extracted from V. xanthia venom was shown to depend on the magnetic field. The yield of ATP produced by enzymes with 24Mg2+ and 26Mg2+ ions in catalytic sites increases by 7-8% at 55 mT and then decreases at 80 mT. For enzyme with 25Mg2+ ion in a catalytic site, the ATP yield increases by 50% and 70% in the fields 55 and 80 mT, respectively. In the Earth field the rate of ATP synthesis by enzyme, in which Mg2+ ion has magnetic nucleus 25Mg, is 2.5 times higher than that by enzymes, in which Mg2+ ion has nonmagnetic, spinless nuclei 24Mg or 26Mg. Both magnetic field effect and magnetic isotope effect demonstrate that the ATP synthesis is an ion-radical process, affected by Zeeman interaction and hyperfine coupling in the intermediate ion-radical pair.     

Effect of 7 mT static magnetic field and iron ions on rat lymphocytes: apoptosis,necrosis and free radical processes

Simultaneous exposure of rat lymphocytes to 7 mT static magnetic field (SMF) and iron ions caused an increase in the number of cells with DNA damage. The mechanism by which MF induces DNA damage and the possible cytotoxic consequences are not known. However, we suppose that free radicals are involved. Potentially, the deterioration of DNA molecules by simultaneous exposure to 7 mT SMF and iron ions may lead to cell death: apoptosis or necrosis. The possible prooxidative properties of these two agents may result in an induction of the lipid peroxidation process as a marker of free radical mechanism in the cells. Experiments were performed on rat blood lymphocytes incubated for 3 h in Helmholtz coils at SMF of flux density 7 mT. During SMF exposure, some samples were treated with ferrous chloride (10 microg/ml), the rest serving as controls. We used the dye exclusion method with the DNA-fluorochromes: ethidium bromide and acridine orange. No significant differences were observed between unexposed lymphocytes incubated with medium alone and lymphocytes exposed to 7 mT SMF. Three-hour incubation with FeCl(2) (10 microg/ml) did not affect cell viability. However, when lymphocytes were exposed to 7 mT SMF and simultaneously treated with FeCl(2), there was a significant increase in the percentage of apoptotic and necrotic cells accompanied by significant alterations in cell viability. As compared to lipid peroxidation, there is a significant increase in the amount of lipid peroxidation end products MDA+4 HNE in rat lymphocytes after simultaneous exposure to 7 mT SMF and FeCl(2) (vs. to the control samples and those exposed to SMF alone). This suggests that 7 mT static magnetic field in the presence of Fe(2+) ions can increase the concentration of oxygen free radicals and thus may lead to cell death.     

Magnetic Field Treatments Improves Sunflower Yield by Inducing Physiological and Biochemical Modulations in Seeds

Magnetic seed enhancement has been practicing as a promising tool to improve germination and seedling growth of low vigor seeds stored under suboptimal conditions, but there is still ambiguity regarding the prospects for magnetism in oilseeds. Present study elucidates the potential of magnetic seed stimulation to improve sunflower germination, growth and yield. Germination and emergence tests were performed to optimize the strength of the magnetic field to sunflower seed enhancement. The seeds were directly exposed to magnetic field strengths of 50, 100 and 150 millitesla (mT) for 5, 10 and 15 min (min) and then standard germination tests were performed. Secondly, the emergence potential of untreated seeds was compared with seed exposed to hydropriming, priming with 3% moringa leaf extract (MLE), priming with magnetically treated water (MTW) for 10 min and priming with 3% MLE solution prepared in magnetically treated water (MTW + MLE). Germination, emergence, seedling growth and seed biochemical properties were used to select the best treatment for field evaluation. The results of the study revealed that magnetic seed treatment with 100 mT for 10 min and seed priming with 3% MLE solution in magnetically treated water (MTW + MLE) significantly improved emergence, crop growth rate and sunflower yield.     

Alleviation of adverse effects of drought stress on growth and some potential physiological attributes in maize (Zea mays L.) by seed electromagnetic treatment

Effects of varying preseed magnetic treatments on growth, chlorophyll pigments, photosynthesis, water relation attributes, fluorescence and levels of osmoprotectants in maize plants were tested under normal and drought stress conditions. Seeds of two maize cultivars were treated with different (T0 [0 mT], T1 [100 mT for 5 min], T2 [100 mT for 10 min], T3 [150 mT for 5 min] and T4 [150 mT for 10 min]) electromagnetic treatments. Drought stress considerably suppressed growth, chlorophyll a and b pigments, leaf water potential, photosynthetic rate (A), stomatal conductance (g(s)) and substomatal CO(2) concentration (C(i)), while it increased leaf glycinebetaine and proline accumulation in both maize cultivars. However, pretreated seeds with different magnetic treatments significantly alleviated the drought-induced adverse effects on growth by improving chlorophyll a, A, E, g(s), C(i) and photochemical quenching and nonphotochemical quenching, while it had no significant effect on other attributes. However, different magnetic treatments negatively affected the g(s) and C(i) particularly in cv. Agaiti-2002 under drought stress conditions. Of all magnetic treatments, 100 and 150 mT for 10 min were most effective in alleviating the drought-induced adverse effects. Overall, preseed electromagnetic treatments could be used to minimize the drought-induced adverse effects on different crop plants.     

On the mitochondrial aspect of reactive oxygen species action in external magnetic fields

Some retinoids or porphyrins can form radical pairs, alter transfer of electrons, and increase synthesis of reactive oxygen species in the mitochondrial respiratory chain. This leads to cell damage and apoptosis. We propose that co-application of an external static magnetic field of several to several hundreds miliTesla (mT) can enhance those effects by further alteration of electron flow in the mitochondrial respiratory chain, facilitation of forbidden transitions from the triplet to the singlet state of retinoid or porphyrin radicals, and modification of radical pair amount. Since electron flow in the mitochondrial respiratory chain seems to possess fractal dynamics, the magnetic field can initiate self- organization of the flow into more regular patterns, and create optimal conditions for damage of cancer cells without any detriment for the normal counterparts. External low magnetic field should improve effectiveness and selectivity of retinoid chemoprevention or porphyrin photodynamic therapy.     

磁场对微生物生长及苯酚降解影响的研究

以Fe3O4磁粉和稳恒弱磁场作为磁场来源,研究了不同磁场条件对微生物/细菌生长及苯酚降解的影响。结果表明,1~4g/L磁粉加量对微生物生长有促进作用,使之提前进入对数增长期;投加量为4g/L时效果最好,加量超过6g/L会抑制微生物生长;磁粉添加使微生物生长静止期稳定性有所下降。适量磁粉和弱磁场作用可促进苯酚与微生物共代谢,能明显提高苯酚的去除率。4g/L磁粉、100mT恒弱磁场作用下,22h对苯酚的去除率分别可达96%、90%,无磁场对照组仅为85%。     

Primary root growth rate of Zea mays seedlings grown in an alternating magnetic field of different frequencies

We have studied the effect of an alternating magnetic field on the growth rate of primary roots in Zea mays. Corn seedlings were grown in the dark, under constant conditions of temperature (25°C) and humidity (100%). They were also subjected to a 5 mT magnetic field, alternating at frequencies of either 5, 10, 20 or 40 Hz. The rate of primary root growth, in plants grown at each frequency, was measured and compared to a control group. Control plants were grown under similar conditions, in the absence of the magnetic field. The growth rate of primary roots in seedlings grown at each of the magnetic field frequencies used, was increased compared to the control group. The highest growth rate was seen in seedlings exposed to a magnetic field alternating at 10 Hz.     

Photochemical primary process of photo-Fries rearrangement reaction of 1-naphthyl acetate as studied by MFE probe

Photo-Fries rearrangement reactions of 1-naphthyl acetate (NA) in n-hexane and in cyclohexane were studied by the magnetic field effect probe (MFE probe) under magnetic fields (B) of 0 to 7 T. Transient absorptions of the 1-naphthoxyl radical, T-T absorption of NA, and a short-lifetime intermediate (τ = 24 ns) were observed by a nanosecond laser flash photolysis technique. In n-hexane, the yield of escaped 1-naphthoxyl radicals dropped dramatically upon application of a 3 mT field, but then the yield increased with increasing B for 3 mT < B≤ 7 T. These observed MFEs can be explained by the hyperfine coupling and the Δg mechanisms through the singlet radical pair. The fact that MFEs were observed for the present photo-Fries rearrangement reaction indicates the presence of a singlet radical pair intermediate with a lifetime as long as several tens of nanoseconds.     

Spin dynamics of the radical pair in a low magnetic field studied by the transient absorption detected magnetic field effect on the reaction yield and switched external magnetic field

The spin dynamics of the radical pair generated from the photocleavage reaction of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TMDPO) in micellar solutions was studied by the time-resolved magnetic field effect (MFE) on the transient absorption (TA) and by a novel technique, absorption detected switched external magnetic field (AD-SEMF). Thanks to the large hyperfine coupling constant (A = 38 mT), a characteristic negative MFE on the radical yield was observed at a magnetic field lower than 60 mT whereas a positive effect due to the conventional hyperfine (HFM) and relaxation mechanisms (RM) was observed at higher magnetic field. The negative effect can be assigned to the mechanism "so-called" low field effect (LFE) mechanism and has been analyzed thoroughly using a model calculation incorporating a fast spin dephasing process. The time scale of the spin mixing process of LFE studied by AD-SEMF is shorter than the lifetime of the recombination kinetics of the radical pair. These results indicate that the LFE originates from the coherent spin motion. This can be interfered from the fast spin dephasing caused by electron spin interaction fluctuations.     

Magnetic modulation of the luminescence of pyrene-N,N-dimethylaniline exciplexes in solutions of reverse micelles

An external magnetic field was found to enhance the luminescence of pyrene-N,N-dimethylaniline exciplexes in a solution of reverse micelles containing water, OT Aerosol, and pentanol (0.6%, B=30 mT). The field dependence of the relative change in the intensity of the exciplex fluorescence does not reach saturation for fields with magnetic induction up to 30 mT, which is not observed in polar homogeneous solutions. These results may be attributed to the circumstance that a significant fraction of pyrene (up to 30%) is localized in the interphase of the reverse micelles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1918–1920, August, 1990.