Lorentz force in water: evidence that hydronium cyclotron resonance enhances polymorphism

Abstract

There is an ongoing question regarding the structure forming capabilities of water at ambient temperatures. To probe for different structures, we studied effects in pure water following magnetic field exposures corresponding to the ion cyclotron resonance of H₃O⁺. Included were measurements of conductivity and pH. We find that under ion cyclotron resonance (ICR) stimulation, water undergoes a transition to a form that is hydroxonium-like, with the subsequent emission of a transient 48.5?Hz magnetic signal, in the absence of any other measurable field. Our results indicate that hydronium resonance stimulation alters the structure of water, enhancing the concentration of EZ-water. These results are not only consistent with Del Giudice's model of electromagnetically coherent domains, but they can also be interpreted to show that these domains exist in quantized spin states.     

Helical water wires

A helitetrahedral model has been proposed to help explain reports of low-frequency oscillations in pure water following electromagnetic excitation at the hydronium ion cyclotron resonance frequency. The Lorentz force and the intrinsic structure constrain the motion of the H₃O⁺ ion so that it enjoys a unique form of proton-hopping, one whose path is helical. This model may also explain the numerous previously observed cyclotron resonance (ICR) biological couplings for cations other than hydronium by merely substituting hydrogen-bonded versions of these for hydronium in the tetrahedral structure. Thus the effectiveness of resonance stimulation in biological systems is explained in terms of the enhanced conductivity and reduced scattering associated with proton-hopping. It is further shown that the addition of charge-balancing hydroxyl ions act to enable oscillatory electric dipole moments that propagate along the helical axis, giving rise to weak power (≈ femtoWatts) radiation patterns. It is conceivable that the radiation associated with this process may play a role in the interactions at the interface between water and living matter.     

NMR structural studies of the bacterial outer membrane protein OmpX in oriented lipid bilayer membranes

The β-barrels found in the outer membranes of prokaryotic and eukaryotic organisms constitute an important functional class of proteins. Here we present solid-state NMR spectra of the bacterial outer membrane protein OmpX in oriented lipid bilayer membranes. We show that OmpX is folded in both glass-supported oriented lipid bilayers and in lipid bicelles that can be magnetically oriented with the membrane plane parallel or perpendicular to the direction of the magnetic field. The presence of resolved peaks in these spectra demonstrates that OmpX undergoes rotational diffusion around an axis perpendicular to the membrane surface. A tightly hydrogen-bonded domain of OmpX resists exchange with D₂O for days and is assigned to the transmembrane β-barrel, while peaks at isotropic resonance frequencies that disappear rapidly in D₂O are assigned to the extracellular and periplasmic loops. The two-dimensional ¹H/¹⁵N separated local field spectra of OmpX have several resolved peaks, and agree well with the spectra calculated from the crystal structure of OmpX rotated with the barrel axis nearly parallel (5° tilt) to the direction of the magnetic field. The data indicate that it will be possible to obtain site-specific resonance assignments and to determine the structure, tilt, and rotation of OmpX in membranes using the solid-state NMR methods that are currently being applied to α-helical membrane proteins.     

The Hydronium Tetrafluoroborate Dimer in Nonpolar Media and its Proton NMR Spectrum

Hydronium tetrafluoroborate ion pairs, H₃O⁺·BF₄ ^- have been shown computationally to be unstable toward decomposition, in the absence of solvation or electrostatic interactions existing in crystals. As the proton NMR spectrum of a hydronium salt with the octanesulfonate-antimony pentachloride complex anion was reported in freon solution, we investigated the hypothesis that larger ionic clusters were present in the nonpolar solvent. It was found that the dimer (H₃O⁺·BF₄ ^-)₂ was stable at the MP2/6-31G* level. GIAO-B3LYP chemical shift calculations with the same basis set and also with the 6-31G**, 6-31++G**, 6-311++G**, dzvp, tzp, tz2p, and qz2p basis sets conducted on the hydronium fluoroborate dimer reproduce the main features of the experimental spectrum: the existence of two signals with a two-to-one intensity ratio and the more intense resonance at higher frequency (more deshielded). The alternative structures, of hydronium tetrafluoroborate ion pairs with one and with two hydrogen bonds between anion and cation, give calculated chemical shifts which are farther from the experimental values.     

Diffusion NMR-based comparison of electrostatic influences of DNA on various monovalent cations

Counterions are important constituents for the structure and function of nucleic acids. Using ⁷Li and ¹³³Cs nuclear magnetic resonance (NMR) spectroscopy, we investigated how ionic radii affect the behavior of counterions around DNA through diffusion measurements of Li⁺ and Cs⁺ ions around a 15-bp DNA duplex. Together with our previous data on ²³Na⁺ and ¹⁵NH₄⁺ ions around the same DNA under the same conditions, we were able to compare the dynamics of four different monovalent ions around DNA. From the apparent diffusion coefficients at varied concentrations of DNA, we determined the diffusion coefficients of these cations inside and outside the ion atmosphere around DNA (D_b and D_f, respectively). We also analyzed ionic competition with K⁺ ions for the ion atmosphere and assessed the relative affinities of these cations for DNA. Interestingly, all cations (i.e., Li⁺, Na⁺, NH₄⁺, and Cs⁺) analyzed by diffusion NMR spectroscopy exhibited nearly identical D_b/D_f ratios despite the differences in their ionic radii, relative affinities, and diffusion coefficients. These results, along with the theoretical relationship between diffusion and entropy, suggest that the entropy change due to the release of counterions from the ion atmosphere around DNA is also similar regardless of the monovalent ion types. These findings and the experimental diffusion data on the monovalent ions are useful for examination of computational models for electrostatic interactions or ion solvation.     

Calcium ion cyclotron resonance in dissipative water structures

Weak magnetic and electromagnetic fields affect physiological processes in animals, plants, and microorganisms. Ion cyclotron resonance (ICR) is discussed as one of the sensitive mechanisms, which enable perception of the geomagnetic field and its orientation. Numerous biological effects are observed involving several small ions, showing windows of predicted frequencies and intensities. The pioneering work of Guiliano Preparata and Emilio Del Giudice using quantum electrodynamics showed that spontaneously originating coherent regions in water facilitate ICR effects at incoherent water phase boundaries. Here we examine the ICR response of the calcium ion (Ca²⁺), crucial for many life processes. We use an aqueous solution containing the biologically ubiquitous membrane lipid L-α-phosphatidylcholine that serves as a biomimetic proxy for dynamic light scattering (DLS) and nonlinear dielectric spectroscopy (NLDS) measurements. One notable result is that this system approaches a new equilibrium upon addition of calcium by means of the oscillatory Belousov–Zhabotinsky chemical reaction, oscillations are significantly reduced under Ca²⁺ ICR application. Secondly an “oscillator” of calcium ions appears to be able to itself couple coherently and predictably to large-scale coherent regions in water. This system appears able to regulate ion fluxes in response to very weak environmental electromagnetic fields.     

Correlation of magnetic AC field on cardiac myocyte Ca2+ transients at different magnetic DC levels

The purpose of this study was to determine the effect of extremely low frequency and weak magnetic fields (WMF) on cardiac myocyte Ca²⁺ transients, and to explore the involvement of potassium channels under the WMF effect. In addition, we aimed to find a physical explanation for the effect of WMF on cardiac myocyte Ca²⁺ transients. Indo‐1 loaded cells, which were exposed to a WMF at 16 Hz and 40 nT, demonstrated a 75 ± 4% reduction in cytosolic Ca²⁺ transients versus control. Treatment with the K_ATP channel blocker, glibenclamide, followed by WMF at 16 Hz exposure, blocked the reduction in cytosolic calcium transients while treatment with pinacidil, a K_ATP channel opener, or chromanol 293B, a selective potassium channel blocker of the delayed rectifier K⁺ channels, did not inhibit the effect. Based on these finding and the ion cyclotron resonance frequency theory, we further investigated the effect of WMF by changing the direct current (DC) magnetic field (B₀). When operating different DC magnetic fields we showed that the WMF value changed correspondingly: for B₀ = 44.5 µT, the effect was observed at 17.05 Hz; for B₀ = 46.5 µT, the effect was observed at 18.15 Hz; and for B₀ = 49 µT the effect was observed at 19.1 Hz. We can conclude that the effect of WMF on Ca²⁺ transients depends on the DC magnetic field level. Bioelectromagnetics 33:634–640, 2012. © 2012 Wiley Periodicals, Inc.     

A Cellular Automata Model of Proton Hopping Down a Channel

Proton hopping is the process where a H‐atom on a hydronium ion forms a H‐bond with the O‐atom of a neighboring H₂O molecule. There is then an exchange of bonding forces when that covalent bond of the H‐atom in the hydronium ion changes to a H‐bond, and the previous H‐bond changes to a covalent bond with the neighboring O‐atom. The neighboring molecule now becomes a hydronium (H₃O⁺) ion. This process repeats itself very rapidly among neighboring hydronium and H₂O molecules. There is a flow of protonic character through bulk H₂O, referred to as proton hopping. This process carries information through living systems where H₂O is present. A cellular automata model of proton hopping down a channel has been created and studied. Variations in the rate of proton entry into the channel and the effects of the polar character of the channel walls was studied using the model. The behavior of the models corresponds to experimental results.     

Nuclear Magnetic Resonance Evidence using D2O for Structured Water in Muscle and Brain

The electric quadrupole moment of the deuterium nucleus provides a nuclear magnetic resonance (NMR) probe of electric field gradients, and thereby of organization of tissue water. 8-17% of H₂O in rat muscle and brain was replaced by D₂O from 50% deuterated drinking water. The peak height of the steady-state NMR spectrum of D in muscle water was 74% lower than that of an equal concentration of D₂O in liquid water. Longitudinal NMR relaxation times (T₁) of D in water of muscle and brain averaged 0.092 and 0.131 sec, respectively, compared with 0.47 sec in D₂O in liquid water. Transverse NMR relaxation times (T₂) averaged 0.009 and 0.022 sec in D₂O of muscle and brain, respectively, compared with 0.45 sec in D₂O in liquid water. These differences cannot be explained by paramagnetic ions or by magnetic inhomogeneities, which leaves increased organization of tissue water as the only tenable hypothesis. Evidence was also obtained that 27% of muscle water and 13% of brain water exist as a separate fraction with T₂ of D₂O less than 2 × 10^-3 sec, which implies an even higher degree of structure. Each of the two fractions may consist of multiple subfractions of differing structure.     

Weak low-frequency electromagnetic oscillations in water

Recent observations of low-frequency electromagnetic oscillations in water suggest an inductive structural component. Accordingly, we assume a helical basis enabling us to model water as an LC tuned oscillator. A proposed tetrahedral structure consisting of three water molecules and one hydronium ion is incorporated into the Boerdijk–Coxeter tetrahelix to form long water chains that are shown to have resonance frequencies consistent with observation. This model also serves to explain separately reported claims of ion cyclotron resonance of hydronium ions, in that the tetrahelix provides a built-in path for helical proton-hopping.     

Electric-field ion cyclotron resonance

We consider the possibility that DC magnetic fields can interact in a resonant manner with endogenous AC electric fields in biological systems. Intrinsic electric-field ion cyclotron resonance (ICR) interactions would be more physically credible than models based on external AC magnetic fields and might be expected as an evolutionary response to the long-term constancy of the geomagnetic field. Bioelectromagnetics 17:85–87, 1997. © 1997 Wiley-Liss, Inc.     

ION cyclotron resonance: Geomagnetic strategy for living systems?

Except for relatively few polarity reversals the magnitude of the magnetic dipole moment of the earth has remained constant since life first began, allowing evolutionary processes to integrate the geomagnetic field (GMF) into several biological functions. One of these, bearing the classical signature of an ion cyclotron resonance (ICR)-like interaction, results in biological change associated with enhanced proton transport. The wide range of cation masses over which this effect is found suggest a fundamental biological dependence on the GMF, one that functions equally well for electric as well as magnetic fields. Such generalization of ICR requires two things: transparency of tissues to the GMF and suitably tuned ELF resonant magnetic or electric fields. To complement the widely reported ICR responses to applied AC magnetic fields, we hypothesize the existence of weak endogenous ICR electric field oscillations within the cell. This equivalence implies that even in the absence of applied AC magnetic fields, biological systems will exhibit intrinsic GMF-dependent ion cyclotron resonance intracellular interactions. Many ICR effects that have been reported appear as antagonist pairs suggesting that the characteristics of the GMF have not only been incorporated into the genome but also appear to function in an endocrine-like manner.     

The temperature dependence of water and counter ion order in soap-water mesophases. A deuterium and sodium NMR study

Deuterium magnetic resonance (DMR) spectra of the water and hydrocarbon chains in potassium and sodium palmitates and sodium magnetic resonance spectra of sodium in sodium palmitate demonstrate correlations between water, hydrocarbon chain and counter ion order. In the lamellar phase of potassium palmitate the order parameters inferred from DMR splittings of D₂O and the first few methylene chain segments initially increase and then decrease with increasing temperature. This is explained in terms of a model where the lipid-water structure at low temperatures imposes a direction for which all the order parameters are smaller than for the higher temperature structure for purely geometric reasons. As temperature increases the structuring effect of water decreases and there is an “apparent” increase in order until at even higher temperatures there is an intrinsic decrease in order parameter. In addition, for potassium palmitate the DMR splittings of D₂O and the first few methylene segments indicate a “phase transition” within the liquid crystalline phase.     

A possible molecular link between the toxicological effects of arsenic,selenium and methylmercury: methylmercury(II) seleno bis(<Emphasis Type="Italic">S</Emphasis>-glutathionyl) arsenic(III)

Using a combination of As and Se K-edge and Hg L_III-edge X-ray absorption spectroscopy, ⁷⁷Se nuclear magnetic resonance spectroscopy, electrospray ionization mass spectrometry and molecular modeling, we have structurally characterized the novel species methylmercury(II) seleno bis(S-glutathionyl) arsenic(III). This species is formed in aqueous solution from CH₃HgOH and the seleno bis(S-glutathionyl) arsinium ion and constitutes an important first step towards characterizing the observed toxicologically relevant interaction between arsenite, selenite and methylmercury which has been previously reported in mammals.     

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

High ionic conductivity of up to 6.4 × 10^?3 S cm^?1 near room temperature (40 °C) in lithium amide‐borohydrides is reported, comparable to values of liquid organic electrolytes commonly employed in lithium‐ion batteries. Density functional theory is applied coupled with X‐ray diffraction, calorimetry, and nuclear magnetic resonance experiments to shed light on the conduction mechanism. A Li₄Ti₅O₁₂ half‐cell battery incorporating the lithium amide‐borohydride electrolyte exhibits good rate performance up to 3.5 mA cm^?2 (5 C) and stable cycling over 400 cycles at 1 C at 40 °C, indicating high bulk and interfacial stability. The results demonstrate the potential of lithium amide‐borohydrides as solid‐state electrolytes for high‐power lithium‐ion batteries.     

On the question of hydronium binding to ATP-synthase membrane rotors

A recently determined atomic structure of an H⁺-coupled ATP-synthase membrane rotor has revived the long-standing question of whether protons may be bound to these structures in the form of a hydronium ion. Using both classical and quantum-mechanical simulations, we show that this notion is implausible. Ab initio molecular dynamics simulations of the binding site demonstrate that the putative H₃O⁺ deprotonates within femtoseconds. The bound proton is thus transferred irreversibly to the carboxylate side chain found in the ion-binding sites of all ATP-synthase rotors. This result is consistent with classical simulations of the rotor in a phospholipid membrane, on the 100-nanosecond timescale. These simulations show that the hydrogen-bond network seen in the crystal structure is incompatible with a bound hydronium. The observed coordination geometry is shown to correspond instead to a protonated carboxylate and a bound water molecule. In conclusion, this study underscores the notion that binding and transient storage of protons in the membrane rotors of ATP synthases occur through a common chemical mechanism, namely carboxylate protonation.     

Primary Ion Depletion Kinetics (PIDK) Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS

We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS), which we name primary ion depletion kinetics (PIDK). PTR-MS is a chemical ionization mass spectrometric (CIMS) technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H₃O⁺, and constant MH⁺. Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H₃O⁺ leads to reduced heating of H₃O⁺ in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N) variation studies). Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (<2% of MH⁺) of the compounds dimethyl sulfide, DMS, a compound that reportedly does not fragment, diethyl sulfide DES, and dipropyl sulfide DPS. And we confirm and complement the results with traditional E/N studies. Summing up, the new approach of primary ion depletion kinetics allows for the identification of dehydrogenation [MH⁺ -H₂] and adduct formation (RMH⁺) as low abundant fragmentation channels in monosulfides.     

Intramolecular general base catalyzed transesterification: The cyclization of ethyl 2-hydroxymethylbenzoate and ethyl 2-hydroxymethyl 4-nitrobenzoate to phthalide and 5-nitrophthalide

The rates of cyclization of ethyl 2-hydroxymethylbenzoate to phthalide have been measured in H₂O at 30°C with μ = 0.5. There is pronounced general base catalysis in the reaction with β = 0.87. The second-order rate constant for imidazole general base catalysis is decreased in D₂O as compared with H₂O by a factor of 3.46. The pH-rate constant profile obtained by extrapolation to zero buffer concentration shows hydronium ion and apparent hydroxide ion catalysis. The value of the second-order rate constant k_OH is 10⁵ greater than k_OH for hydrolysis of ethyl benzoate. Ethyl 2-hydroxymethyl 4-nitrobenzoate cyclizes to 5-nitrophthalide in a similar manner. The Brönsted coefficient β for general base catalysis is 0.97, within error of unity. Thus, it is probable that general base catalysis involves rate-determining proton transfer.     

Impact of lung density on isolated lung tumor dose in VMAT using inline MR-Linac

PurposeThis study investigated the impact of lung density on the isolated lung tumor dose for volumetric modulated arc therapy (VMAT) in an inline magnetic resonance linear accelerator (MR-Linac) using the Monte Carlo (MC) simulation.MethodsCT images of the thorax phantoms with lung tumors of 1, 2, and 3 cm diameters were converted into voxel-base phantoms with lung densities of 0.1, 0.2, and 0.3 g/cm³, respectively. The dose distributions were calculated for partial-arc VMAT. The dose distributions were compared using dose differences, dose volume histograms, and dose volume indices.ResultsIn all cases, the inline magnetic field significantly enhanced the lung tumor dose compared to that at 0 T. For the 1 cm lung tumor, the inline magnetic field of 1 T increased the minimum dose of 95% of the Planning target volume (PTV D₉₅) by 14.0% in 0.1 g/cm³ lung density as compared to that in 0.3 g/cm³ at 0 T. In contrast, at 0 and 0.5 T, the PTV D₉₅ in 0.3 g/cm³ lung density was larger than that in lung density of 0.1 g/cm³. For the 2 cm lung tumor, a similar tendency to 1 cm was observed, whereas the dose impact of lung density was smaller than that for 1 cm. For the 3 cm lung tumor, the lung tumor dose was independent of lung density at 0.5 T and 1.0 T.ConclusionThe inline MR-Linac with the magnetic field over 1 T can enhance the PTV D₉₅ for VMAT regardless of the lung density.