Effects of 100 GHz radiation on alkaline phosphatase activity and antigen–antibody interaction

Equipment that generates microwave radiation (MWR) spanning the frequency range of 300 MHz–100 GHz is becoming more common. While MWR lacks sufficient energy to break chemical bonds, the disagreement as to whether MWR exposure is detrimental to cellular dysfunction may be difficult to clarify using complex systems such as whole animals, cells, or cell extracts. Recently, the high frequency range of terahertz (THz) radiation has been explored and sources of radiation and its detectors have been developed. THz radiation is associated with the frequency interval from 100 GHz to 20 THz and constitutes the next frontier in imaging science and technology. In the present study, we investigated the effect of radiation in the low frequency THz range (100 GHz) on two defined molecular interactions. First, the interaction of soluble or immobilized calf alkaline phosphatase with the substrate p‐nitrophenylphosphate and second, the interaction between an antibody (mouse monoclonal anti‐DNP) and its antigen (DNP). Irradiation of enzyme either prior to addition of substrate or during the enzymatic reaction resulted in small but significant reductions in enzyme activity. These differences were not observed if the enzyme had previously been immobilized onto plastic microwells. Exposure of immobilized antigen to radiation did not influence the ability of the antigen to interact with antibody. However, irradiation appeared to decrease the stability of previously formed antigen–antibody complexes. Our data suggest that 100 GHz radiation can induce small but statistically significant alterations in the characteristics of these two types of biomolecular interactions. Bioelectromagnetics 30:167–175, 2009. © 2008 Wiley‐Liss, Inc.     

Studies on luminescence from a cerium‐doped strontium stannate phosphor

The crystal structure and morphology of Ce³⁺‐doped SrSnO₃ materials prepared using the solid‐state reaction method were extensively characterized using experimental techniques. X‐Ray diffraction results show that the cerium substitution of strontium does not change the structure of the strontium stannate. Raman spectroscopy was used to investigate the microstructures and lattice vibrations. Environmental scanning electron microscopy images showed that phosphors aggregate and their particles form irregular shapes. SrSnO₃ exhibits an intense green emission with a broad band originating from the 5d¹ → 4f¹ transition of cerium. It was observed that, after exposure to beta‐irradiation, the glow curve of this material has two broad thermoluminescence peaks, one centered at ~ 127°C and the other at ~ 245°C for a heating rate of 5 K/s. The kinetic parameters, which include the frequency factor and the activation energy of the material, were calculated using Chen's method, after beta‐irradiation. The fading and reusability of the phosphor were also studied and it was found that the phosphor is suitable for radiation dosimetry. Copyright © 2014 John Wiley & Sons, Ltd.     

Microstructural and Electronic Origins of Open‐Circuit Voltage Tuning in Organic Solar Cells Based on Ternary Blends

Organic ternary heterojunction photovoltaic blends are sometimes observed to undergo a gradual evolution in open‐circuit voltage (V_oc) with increasing amounts of a second donor or an acceptor. The V_oc is strongly correlated with the energy of the charge transfer state in the blend, but this value depends on both local and mesoscopic orders. In this work, the behavior of V_oc in the presence of a wide range of interfacial electronic states is investigated. The key charge transfer state interfaces responsible for V_oc in several model systems with varying morphology are identified. Systems consisting of one donor with two fullerene molecules and of one acceptor with a donor polymer of varying regio‐regularity are used. The effects from the changing energetic disorder in the material and from the variation due to a law of simple mixtures are quantified. It has been found that populating the higher‐energy charge transfer states is not responsible for the observed change in V_oc upon the addition of a third component. Aggregating polymers and miscible fullerenes are compared, and it has been concluded that in both cases charge delocalization, aggregation, and local polarization effects shift the lowest‐energy charge transfer state distribution.     

Evolution of Hot Polaron States with a Nanosecond Lifetime in a Manganite Perovskite

Understanding and controlling the relaxation process of optically excited charge carriers in solids with strong correlations is of great interest in the quest for new strategies to exploit solar energy. Usually, optically excited electrons in a solid thermalize rapidly on a femtosecond to picosecond timescale due to interactions with other electrons and phonons. New mechanisms to slow down thermalization will thus be of great significance for efficient light energy conversion, e.g., in photovoltaic devices. Ultrafast optical pump–probe experiments in the manganite Pr_0.65Ca_0.35MnO_3, a photovoltaic, thermoelectric, and electrocatalytic material with strong polaronic correlations, reveal an ultraslow recombination dynamics on a nanosecond‐time scale. The nature of long living excitations is further elucidated by photovoltaic measurements, showing the presence of photodiffusion of excited electron–hole polaron pairs. Theoretical considerations suggest that the excited charge carriers are trapped in a hot polaron state. Escape from this state is possible via a slow dipole‐forbidden recombination process or via rare thermal fluctuations toward a conical intersection followed by a radiation‐less decay. The strong correlation between the excited polaron and the octahedral dynamics of its environment appears to be substantial for stabilizing the hot polaron.     

Thermodynamic Efficiency Limit of Molecular Donor‐Acceptor Solar Cells and its Application to Diindenoperylene/C60‐Based Planar Heterojunction Devices

In organic photovoltaic (PV) cells, the well‐established donor‐acceptor (D/A) concept enabling photo‐induced charge transfer between two partners with suitable energy level alignment has proven extremely successful. Nevertheless, the introduction of such a heterojunction is accompanied with additional energy losses as compared to an inorganic homojunction cell, owing to the presence of a charge‐transfer (CT) state at the D/A interface. Based on the principle of detailed balance, a modified Shockley‐Queisser theory is developed including the essential effects of interfacial CT states, that allows for a quantitative assessment of the thermodynamic efficiency limits of molecular D/A solar cells. Key parameters, apart from the optical gap of the absorber material, entering the model are the energy (E_CT) and relative absorption strength (α_CT) of the CT state. It is demonstrated how the open‐circuit voltage (V_OC) and thus the power conversion efficiency are affected by different parameter values. Furthermore, it is shown that temperature dependent device characteristics can serve to determine the CT energy, and thus the upper limit of V_OC for a given D/A combination, as well as to quantify non‐radiative recombination losses. The model is applied to diindenoperylene (DIP)‐based photovoltaic devices, with open‐circuit voltages between 0.9 and 1.4 V, depending on the partner, that have recently been reported.     

Effects of millimeter waves on ionic currents of Lymnaea neurons

The effects of mm‐waves 60.22–62.22 GHz and 75 GHz on A‐type K⁺ currents and the effects of 61.22 GHz on Ca²⁺ currents of Lymnaea neurons were investigated using a whole‐cell voltage‐clamp technique. The open end of a rectangular waveguide covered with a thin Teflon film served as a radiator. Specific absorption rates at the waveguide outlet, inserted into physiological solution, were in the range of 0–2400 W/kg. Millimeter wave irradiation increased the peak amplitudes, activation rates, and inactivation rates of both ion currents. The changes in A‐type K⁺ current were not dependent on the irradiation frequency. It was shown that the changes in the amplitudes and kinetics of both currents resulted from the temperature rise produced by irradiation. No additional effects of irradiation on A‐type K⁺ current other than thermal were found when tested at the phase transition temperature or in the presence of ethanol. Ethanol reduced the thermal effect of irradiation. Millimeter waves had no effect on the steady‐state activation and inactivation curves, suggesting that the membrane surface charge and binding of calcium ions to the membrane in the area of channel locations did not change. Bioelectromagnetics 20:24–33, 1999. © 1999 Wiley‐Liss, Inc.     

Ni‐Metalloid (B,Si, P,As, and Te) Alloys as Water Oxidation Electrocatalysts

Breakthroughs toward effective water‐splitting electrocatalysts for mass hydrogen production will necessitate material design strategies based on unexplored material chemistries. Herein, Ni‐metalloid (B, Si, P, As, Te) alloys are reported as an emergent class of highly promising electrocatalysts for the oxygen evolution reaction (OER) and insight is offered into the origin of activity enhancement on the premise of the surface electronic structure, the OER activation energy, influence of the guest metalloid elements on the lattice structure of the host metal (Ni), and surface‐oxidized metalloid oxoanions. The metalloids modify the lattice structure of Ni, causing changes in the nearest Ni–Ni interatomic distance (d_Ni–Ni). The activation energy E_a scales with d_Ni–Ni indicating an apparent dependence of the OER activity on lattice properties. During the OER, surface Ni atoms are oxidized to nickel oxyhydroxide, which is the active state of the catalyst, meanwhile, the surface metalloids are oxidized to the corresponding oxoanions that affect the interfacial electrode/electrolyte properties and hence the adsorption/desorption interaction energies of the reacting species.     

An Air‐Stable and Dendrite‐Free Li Anode for Highly Stable All‐Solid‐State Sulfide‐Based Li Batteries

Li metal is a promising anode material for all‐solid‐state batteries, owing to its high specific capacity and low electrochemical potential. However, direct contact of Li metal with most solid‐state electrolytes induces severe side reactions that can lead to dendrite formation and short circuits. Moreover, Li metal is unstable when exposed to air, leading to stringent processing requirements. Herein, it is reported that the Li₃PS₄/Li interface in all‐solid‐state batteries can be stabilized by an air‐stable Li_xSiS_y protection layer that is formed in situ on the surface of Li metal through a solution‐based method. Highly stable Li cycling for over 2000 h in symmetrical cells and a lifetime of over 100 cycles can be achieved for an all‐solid‐state LiCoO₂/Li₃PS₄/Li cell. Synchrotron‐based high energy X‐ray photoelectron spectroscopy in‐depth analysis demonstrates the distribution of different components within the protection layer. The in situ formation of an electronically insulating Li_xSiS_y protection layer with highly ionic conductivity provides an effective way to prevent Li dendrite formation in high‐energy all‐solid‐state Li metal batteries.     

Analyzing the effect of homogeneous frustration in protein folding

The energy landscape theory has been an invaluable theoretical framework in the understanding of biological processes such as protein folding, oligomerization, and functional transitions. According to the theory, the energy landscape of protein folding is funneled toward the native state, a conformational state that is consistent with the principle of minimal frustration. It has been accepted that real proteins are selected through natural evolution, satisfying the minimum frustration criterion. However, there is evidence that a low degree of frustration accelerates folding. We examined the interplay between topological and energetic protein frustration. We employed a C_α structure‐based model for simulations with a controlled nonspecific energetic frustration added to the potential energy function. Thermodynamics and kinetics of a group of 19 proteins are completely characterized as a function of increasing level of energetic frustration. We observed two well‐separated groups of proteins: one group where a little frustration enhances folding rates to an optimal value and another where any energetic frustration slows down folding. Protein energetic frustration regimes and their mechanisms are explained by the role of non‐native contact interactions in different folding scenarios. These findings strongly correlate with the protein free‐energy folding barrier and the absolute contact order parameters. These computational results are corroborated by principal component analysis and partial least square techniques. One simple theoretical model is proposed as a useful tool for experimentalists to predict the limits of improvements in real proteins.Proteins 2013; 81:1727–1737. © 2013 Wiley Periodicals, Inc.     

Exploiting Lithium‐Depleted Cathode Materials for Solid‐State Li Metal Batteries

Solid‐state lithium metal batteries (SSLMBs) may become one of the high‐energy density storage devices for the next generation of electric vehicles. High safety and energy density can be achieved by utilizing solid electrolytes and Li metal anodes. Therefore, developing cathode materials which can match with Li metal anode efficiently is indispensable. In SSLMBs, Li metal anodes can afford the majority of active lithium ions, then lithium‐depleted cathode materials can be a competitive candidate to achieve high gravimetric energy density as well as save lithium resources. Li_0.33MnO₂ lithium‐depleted material is chosen, which also has the advantages of low synthesis temperature and low cost (cobalt‐free). Notably, solid‐state electrolyte can greatly alleviate the problem of manganese dissolution in the electrolyte, which is beneficial to improve the cycling stability of the battery. Thus, SSLMBs enable practical applications of lithium‐depleted cathode materials.     

Realizing Reversible Conversion‐Alloying of Sb(V) in Polyantimonic Acid for Fast and Durable Lithium‐ and Potassium‐Ion Storage

Finding suitable electrode materials for alkali‐metal‐ion storage is vital to the next‐generation energy‐storage technologies. Polyantimonic acid (PAA, H₂Sb₂O₆ · nH₂O), having pentavalent antimony species and an interconnected tunnel‐like pyrochlore crystal framework, is a promising high‐capacity energy‐storage material. Fabricating electrochemically reversible PAA electrode materials for alkali‐metal‐ion storage is a challenge and has never been reported due to the extremely poor intrinsic electronic conductivity of PAA associated with the highest oxidation state Sb(V). Combining nanostructure engineering with a conductive‐network construction strategy, here is reported a facile one‐pot synthesis protocol for crafting uniform internal‐void‐containing PAA nano‐octahedra in a composite with nitrogen‐doped reduced graphene oxide nanosheets (PAA?N‐RGO), and for the first time, realizing the reversible storage of both Li⁺ and K⁺ ions in PAA?N‐RGO. Such an architecture, as validated by theoretical calculations and ex/in situ experiments, not only fully takes advantage of the large‐sized tunnel transport pathways (0.37 nm²) of PAA for fast solid‐phase ionic diffusion but also leads to exponentially increased electrical conductivity (3.3 S cm^?1 in PAA?N‐RGO vs 4.8 × 10^?10 S cm^?1 in bare‐PAA) and yields an inside‐out buffer function for accommodating volume expansion. Compared to electrochemically irreversible bare‐PAA, PAA?N‐RGO manifests reversible conversion‐alloying of Sb(V) toward fast and durable Li⁺‐ and K⁺‐ion storage.     

Microwave absorption by magnetite: A possible mechanism for coupling nonthermal levels of radiation to biological systems

The presence of trace amounts of biogenic magnetite (Fe₃O₄) in animal and human tissues and the observation that ferromagnetic particles are ubiquitous in laboratory materials (including tissue culture media) provide a physical mechanism through which microwave radiation might produce or appear to produce biological effects. Magnetite is an excellent absorber of microwave radiation at frequencies between 0.5 and 10.0 GHz through the process of ferromagnetic resonance, where the magnetic vector of the incident field causes precession of Bohr magnetons around the internal demagnetizing field of the crystal. Energy absorbed by this process is first transduced into acoustic vibrations at the microwave carrier frequency within the crystal lattice via the magnetoacoustic effect; then, the energy should be dissipated in cellular structures in close proximity to the magnetite crystals. Several possible methods for testing this hypothesis experimentally are discussed. Studies of microwave dosimetry at the cellular level should consider effects of biogenic magnetite. © 1996 Wiley-Liss, Inc.     

FeS2‐Imbedded Mixed Conducting Matrix as a Solid Battery Cathode

A new concept of pairing an active material and a mixed conductor is explored as a solid‐state battery electrode. By imbedding nano‐FeS₂ domains into an amorphous LiTiS₂ matrix, a hybrid power‐energy system is achieved while additionally improving upon many common solid electrode design flaws. High‐resolution transmission electron microscopy is used to probe the active material/mixed conductor interface over the course of cycling. Arguably the most beneficial development is enhancement of charge transfer, manifesting in a significantly increased exchange current as captured in a Tafel analysis. By developing a solution to active material isolation and creating a more homogenous electrode design, cycling at a high rate of C/2 for 500 cycles is obtained. Additionally, the electrode can recover full capacity simply by reducing system rate. Capacity recovery implicates a lack of active material isolation, a common problem in solid‐state batteries.     

Ammonium formate, a compound for sensitive EPR dosimetry

Alanine EPR dosimetry has been applied successfully when measuring intermediate and high radiation doses. Although the performance of alanine dosimetry is being improved, the sensitivity of the material is too low for a fast and simple low- dose determination. Here we present the results using ammonium formate as an EPR dosimeter material. Ammonium formate is seven times more sensitive than alanine, using spectrometer settings optimized for the latter. Deuterated ammonium formate is found to be more than eight times more sensitive than alanine. Analysis of signal stability with time shows that the ammonium formate signal is stable by 5 min after irradiation and that no change in signal intensity is found during 8 days. The atomic composition of ammonium formate is closer to that of tissue than alanine, and thus the energy dependence is smaller than that of alanine at photon energies below 200 keV. Power saturation studies indicate that the energy transfer between the spins and the lattice is fast in ammonium formate, which gives the possibility of using high microwave power without saturation to further increase the sensitivity. These results suggest that ammonium formate has some important properties required of an EPR dosimeter for applications in dosimetry in the dose range typical for radiation therapy.     

The effect of a 94 GHz electromagnetic field on neuronal microtubules

Hardware that generates electromagnetic waves with wavelengths from 1 to 10 mm (millimeter waves, “MMW”) is being used in a variety of applications, including high‐speed data communication and medical devices. This raises both practical and fundamental issues concerning the interaction of MMW electromagnetic fields (EMF) with biological tissues. A 94 GHz EMF is of particular interest because a number of applications, such as active denial systems, rely on this specific frequency. Most of the energy associated with MMW radiation is absorbed in the skin and, for a 94 GHz field, the power penetration depth is shallow (≈0.4 mm). At sufficiently high energies, skin heating is expected to activate thermal pain receptors, leading to the perception of pain. In addition to this “thermal” mechanism of action, a number of “non‐thermal” effects of MMW fields have been previously reported. Here, we investigated the influence of a 94 GHz EMF on the assembly/disassembly of neuronal microtubules in Xenopus spinal cord neurons. We reasoned that since microtubule array is regulated by a large number of intracellular signaling cascades, it may serve as an exquisitely sensitive reporter for the biochemical status of neuronal cytoplasm. We found that exposure to 94 GHz radiation increases the rate of microtubule assembly and that this effect can be entirely accounted for by the rapid EMF‐elicited temperature jump. Our data are consistent with the notion that the cellular effects of a 94 GHz EMF are mediated entirely by cell heating. Bioelectromagnetics 34:133–144, 2013. © 2012 Wiley Periodicals, Inc.     

Dy(3+) and Mn(2+) emission in fluoride- and chloride-based Na(3) (SO(4) )X (X = F or Cl) phosphors

In the present study, Na₃(SO₄)X (X = F or Cl) halosulphate phosphors have been synthesized by the solid‐state diffusion method. The phase formation of the compounds Na₃(SO₄)F and Na₃(SO₄)Cl were confirmed by X‐ray powder diffraction (XRD) measurement. Photoluminescence (PL) excitation spectrum measurement of Na₃(SO₄)F:Ce³⁺ and Na₃(SO₄)Cl:Ce³⁺ shows this phosphor can be efficiently excited by near‐ultraviolet (UV) light and presents a dominant luminescence band centred at 341 nm for Ce³⁺, which is responsible for energy transfer to Dy³⁺and Mn²⁺ ions. The efficient Ce³⁺ → Dy³⁺ energy transfer in Na₃(SO₄)F and Na₃(SO₄)Cl under UV wavelength was observed due to ⁴ F_9/2 to ⁶H_15/2 and ⁶H_13/2 level, while Ce³⁺ → Mn²⁺ was observed due to ⁴ T₁ state to ⁶A₁. The purpose of the present study is to develop and understanding the photoluminescence properties of Ce³⁺‐, Dy³⁺‐ and Mn²⁺‐doped fluoride and chloride Na₃(SO₄)X (X = F or Cl) luminescent material, which can be the efficient phosphors in many applications, such as scintillation applications, TL dosimetry and the lamp industry, etc. Copyright © 2012 John Wiley & Sons, Ltd.     

New structural–optical effect in LiF–Li2B4O7 thin-film structures in the crystallization

The effect of optical radiation during the phase transition from the amorphous to the crystalline state of matter was investigated for the first time. The results were obtained on nanoscale films of (LiF)_x(Li₂B₄O₇)_1-x compositions by sputtering on cold Ni substrates. The starting materials for films were chosen due to their wide use for tissue-equivalent ionizing radiation dosimetry. It is shown that the detected thermoluminescence effect is sensitive to the thickness of the films. The paper compares the results of these studies with the study of the thermoluminescence characteristics of films irradiated by an M-30 microtron with bremsstrahlung radiation with a maximum energy of 6 MeV. The absorbed radiation dose was 1 kGy. Differences in the luminescence characteristics of irradiated and nonirradiated films were revealed. The nature of the demonstrated structural–optical effect is discussed.     

SAR versus Sinc: What is the appropriate RF exposure metric in the range 1–10 GHz? Part II: Using complex human body models

This is the second of the two articles that present modeling data and reasoned arguments for specifying the appropriate crossover frequency at which incident power flux density (S_inc) replaces the peak 10 g averaged value of the specific energy absorption rate (SAR) as the designated basic restriction for protecting against radiofrequency electromagnetic heating effects in the 1–10 GHz range. In our first study, we compared the degree of correlation between these basic restrictions and the peak‐induced tissue temperature rise (ΔT) for a representative range of population/exposure scenarios using simple multi‐planar models exposed to plane wave conditions. In this complementary study, complex heterogeneous head models for an adult and 12‐year‐old child were analyzed at 1, 3, 6, 8, and 10 GHz for a variety of exposure conditions. The complex models indicate that peak ΔT is better correlated with peak 10 g SAR than S_inc at 1 and 3 GHz and with S_inc at 6–10 GHz, in contrast to the results from Part I. Considering the planar and complex body modeling results together, and given the equivocal indications of the two metrics in the 6–10 GHz range, we recommend that the breakpoint be set at 6 GHz. This choice is also based on other considerations such as ease of assessment. We also recommend that the limit level of S_inc should be adjusted to provide a better match with 10 g SAR in the induced tissue temperature rise. Bioelectromagnetics 31:467–478, 2010. © 2010 Wiley‐Liss, Inc.     

Surface Mn Oxidation State Controlled Spinel LiMn2O4 as a Cathode Material for High‐Energy Li‐Ion Batteries

Spinel lithium manganese oxide (LiMn₂O₄) has attracted much attention as a promising cathode material for large‐scale lithium ion batteries. However, its continuous capacity fading at elevated temperature is an obstacle to extended cycling in large‐scale applications. Here, surface Mn oxidation state controlled LiMn₂O₄ is synthesized by coating stoichiometric LiMn₂O₄ with a cobalt‐substituted spinel, for which stoichiometric LiMn₂O₄ is used as the starting material and onto which a Li_xMn_yCo_zO₄ layer is coated from an acetate‐based precursor solution. In the coated material, the concentrations of both cobalt and Mn⁴⁺ ions vary from the surface to the core. the former without any lattice mismatch between the coating layer and host material. Cycle tests are performed under severe conditions, namely, high temperature and intermittent high current load. During the first discharge cycle at 7 C and 60 °C, a high energy and power density are measured for the coated material, 419 and 3.16 Wh kg^?1, respectively, compared with 343 and 3.03 Wh kg^?1, respectively, for the bare material. After 65 cycles under severe conditions, the coated material retains 82% and ≈100% of the initial energy and power density, respectively, whereas the bare material retains only ≈68% and ≈97% thereof.