Self-Aggregation and Orientation of the Ion Channel-Forming Zervamicin IIA in the Membranes of ePC Vesicles Studied by cw EPR and ESEEM Spectroscopy

The ion channel-forming peptide antibiotic zervamicin A was studied in egg phosphocholin lipid membranes of large multilamellar vesicles (LMV) at 77 K. Continuous wave electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) methods combined with site-specific electron spin labeling were used to study the aggregation and immersion depth of two analog molecules, i.e., each monolabeled either at the N- or C-terminal end of the helical molecule. Analysis of the shape of the EPR spectra indicates that zervamicin molecules form aggregates in which the dipolar interaction between the spin labels at the N-terminus is substantially larger than that between the labels at the C-terminus. The ESEEM method was used to study the interaction between the nitroxide radical spin labels of the zervamicin molecules and deuterium nuclei in LMV, which were prepared using a D₂O buffer. It is established that the largest amplitude of deuterium modulation of the unpaired electron is observed for zervamicin molecules labeled at the N-terminus. Based on the analysis of the Fourier parameters of the deuterium modulated spectrum, a model of the immersion depth of the terminal ends of the zervamicin molecule in a lipid bilayer is formulated. All of the spin labels at the N-terminus are grouped at the lipid–water interface, whereas 60% of labels at the C-terminus are located at the lipid–water interface and 40% are more deeply inserted into the lipid bilayer.     

Determination of the deuterium content of deuterated betaine arsenate by electron spin echo envelope modulation

An alternative method for the determination of the deuterium content in the hydrogen bonds of ferroelectric/antiferroelectric deuterated betaine arsenate is presented. Carbon radicals formed by gamma irradiation of the betaine arsenate have been used as paramagnetic probes. The deuterium content in the hydrogen bonds has been determined by analyzing the modulation in the electron spin echo spectra of the carbon radical (CH₃)₃N+CHCOO^? which arises because of the dipolar interactions between the paramagnetic radical and the deuterium nuclei.     

Rescaling of 2D ESEEM Data as a Tool for Inverse Problem Solving

A rescaling procedure is proposed for electron spin echo envelope modulation spectra observed at several electron paramagnetic resonance transitions. Analytical expressions describing the relations between the rescaled frequencies and hyperfine and quadrupole parameters of the remote nucleus are obtained. The dependences of the rescaled data on the external magnetic field and spin projections of the ion nucleus and the remote nuclei are used to derive the parameters of the nuclear state in the crystals Y₂SiO₅ and YVO₄ doped by ion Nd³⁺.     

ESEEM Measurements of Local Water Concentration in D<Subscript>2</Subscript>O-Containing Spin-Labeled Systems

To calibrate electron spin echo envelope modulation (ESEEM) amplitudes with respect to the deuterium water content in spin-labeled biological systems, ESEEM of nitroxide TEMPO has been studied in frozen glassy D₂O-dimethylsulfoxide mixtures of different composition. The interaction between the unpaired electron of nitroxide and the deuterium nuclei manifests itself in a cosine Fourier transform spectrum as the sum of a narrow line with the doublet quadrupole splitting and of a broad one. The narrow line arises from interaction with distant deuterium nuclei, the broad one arises from interaction with nearby nuclei belonging to nitroxide-water molecule complexes. The dependence on water concentration was found to be nonlinear for the intensity of the narrow line and close to linear for the intensity of the quadrupole doublet. Therefore, the intensity of the quadrupole doublet is suggested as a measure of concentration of free water around a spin label in biological objects. Fourier transform line shape was theoretically simulated for different model distributions of water molecules around the spin label. Simulations confirm the linear dependence of the quadrupole doublet intensity on water concentration seen in the experiment. The suggested approach was applied to analyze data for spin-labeled dipalmitoylphosphatidylcholine (DPPC) and DPPC-cholesterol D₂O-hydrated model membranes. The concentration of free water near the spin-labeled fourth carbon atom along the lipid chain was estimated as 5.2 and 7.2 M for DPPC and DPPC-cholesterol membranes, respectively. Authors’ address: Sergei Dzuba, Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, Institutskaya 3, 630090 Novosibirsk, Russian Federation     

Q-switched and continuous-wave mode-locking of a diode-pumped Nd:Gd0.64Y0.36VO4−Cr4+:YAG laser

We report on a diode-pumped passively mode-locked Nd:Gd_0.64Y_0.36VO₄ laser with a Cr⁴⁺:YAG saturable absorber. Q-switched mode locking (QML) with 90% modulation depth was obtained. The peak power of the mode-locked pulse near the maximum of the Q-switched envelope was estimated to be about 1.7 MW at the pump power of 12 W. Besides QML, continuous-wave mode locking was also experimentally realized, for the first time to our knowledge, in the laser under a strong intracavity pulse energy fluence. The mode-locked pulse width is about 2.96 ps at a repetition rate of 161.3 MHz.     

Electron spin-lattice relaxation of Yb3+ and Gd3+ ions in glasses

The electron spin-lattice relaxation rate (T ₁ ^?1) was measured in two glass samples: (i) a phosphate glass doped with 1 wt% Yb₂O₃ and (ii) a Li₂Si₄O₉ glass sample doped with 0.2 wt% Gd₂O₃. In the Yb³⁺-doped glass sample,T ₁ was measured by an electron-spin-echo technique from 4.2 to 6 K, by the modulation method from 10 to 26 K and by the EPR linewidth from 30 to 100 K. It was found thatT ₁ ^?1 αT ⁿ withn=9 in the range 4.2–6 K.n decreased gradually as the temperature was increased and tended towards 2 above 40 K. Over the entire temperature range 4.2–100 K,T ₁ ^?1 was fitted toAT+BT ⁹ J ₈ (Θ _D/T) (whereA andB are two temperature-independent constants,J ₈ is the well-known Van Vleck integral andΘ _D is the Debye temperature). The value ofΘ _D (=46.3±0.9 K) so determined is in good agreement with that of Stevens and Stapleton from theirT ₁ measurements in the range 1.5 to 7 K. In the Gd³⁺-doped glass, it was observed thatT ₁ ^?1 αT over the range 50–150 K. The data for Ye³⁺-doped glass sample were accounted for by assuming that the phonon modulation of the ligand field is the dominant mechanism, associated with a low Debye temperature in accordance with the published data obtained by using other techniques to study lattice dynamics. On the other hand, the data on the Gd³⁺-doped glass sample were explained to be predominantly due to a mechanism involving Two-Level-Systems (TLS)     

An experimental approach to the analysis of electric field gradients in ionic crystals

The spectrum of a partially oriented sample of ethanol has been analysed by making use of the simpler spectra obtained from the species CD₃CH₂OH and CH₃CD₂OH, together with ¹H?{²H} double resonance. With p-ethoxy-benzylidene-p-n-butylaniline (EBBA) as the nematic solvent the dipolar couplings of CH₃ and CH₂ protons with the OH proton can be observed, and their magnitudes are compared with values calculated assuming different models for C-O-H internal rotation. Information on the quadrupole coupling constant tensor elements for CD₃ and CD₂ deuterium nuclei is obtained.     

LD-pumped 1.34 μm-Q-switched and mode-locked Nd:GdVO4 laser by a V3+:YAG saturable absorber

A diode-pumped passively Q-switched and mode-locked Nd:GdVO₄ laser at 1.34 μm with V³⁺:YAG as the saturable absorber is realized in a V-type folded cavity. About 100% modulation depth of mode locking can be obtained as long as the pump power reaches the oscillation threshold. The width of the mode-locked pulse is estimated to be less than 280 ps with 200 MHz repetition rate within an about 980 ns-long Q-switched pulse envelope. A maximum output power of 200 mW and Q-switched pulse energy of 5.7 μJ is obtained.     

Secondary ion mass spectrometry measurements of deuterium penetration into silicon by low pressure RF glow discharges

Abstract

Using secondary ion mass spectrometry (SIMS) the penetration of deuterium into Si(100) substrates as a result of exposure to deuterium low pressure rf discharges has been determined as a function of exposure time, thermal contact of the Si wafers to the substrate electrode, substrate doping, and discharge pressure. For undoped (100) single crystal Si exposed without intentional heating to a 25 m torr D₂ plasma for 1 min the deuterium concentration in the near-surface region (0—30 nm) approaches 10²¹ at.cm^?3. It drops off with depth, but is still greater than 10¹⁷ at.cm.^?3 at a silicon depth of 200 nm. The large penetration depth, the observation that lowering the substrate temperature decreases the rate of deuterium uptake, and the dependence of deuterium penetration on the substrate doping type indicate that hydrogen diffusion is of primary importance. The presence of a 50 nm thick oxide layer on the Si substrate during plasma exposure lowers the deuterium near-surface concentration in the Si substrate by about three orders of magnitude, while the presence of 10 nm of thermal oxide reduces the deuterium uptake only insignificantly. Heavily B and As doped polycrystalline Si show less deuterium penetration, while undoped polycrystalline Si shows more deuterium uptake than undoped single crystal Si for the same plasma treatment.     

Electron spin echo at S-band: Nuclear modulations and decay in C60 powder

At S-band (≈ 3 GHz) the modulation amplitude of the Electron Spin Echo patterns is increased with respect to the amplitude at X-band: as a consequence, it is possible to reveal the presence of nuclei not detectable at X-band. In this paper the results obtained by running ESE experiments at S-band on a C₆₀ powder sample containing radicals are shown and discussed. The two- and three-pulse Electron Spin Echo patterns exhibit both¹³C modulation and proton modulation not detected at X-band. The experimental data are quantitatively analyzed by simulating the time-domain patterns and their Fourier transforms. It results that a noticeable amount of proton nuclei surrounds the intrinsic paramagnetic centers. On the basis of the analysis, a possible explanation of their existence is given.     

Experimental study on passively Q-switched mode-locking diode-pumped Nd:KGW laser with Cr4+:YAG

A diode-pumped passively Q-switched and mode-locked Nd:KGW/Cr⁴⁺:YAG laser with different output couples is realized in a V-type folded cavity. About 85% modulation depth for the mode-locked pulses has been obtained. The repetition rate of the mode-locked pulses inside the Q-switched envelope was about 798 MHz.     

Simultaneous mode locking in an acousto-optic Q-switched Nd:LuVO4 laser

Simultaneous mode locking had been obtained in acousto-optic Q-switched Nd:LuVO₄ laser by using a Z-type cavity. Pulses with great average output power and narrow pulse width were observed in our experiment. The modulation depth is nearly 90% and the width of Q-switched envelope is about 70 ns, and both maintained constant with the increase of pump power. The maximum average output power of 1.83 W was obtained when the incident pump power was 6.78 W and the Q-switched envelop repetition frequency was 30 kHz. Also the average pulse width of the mode locking among the Q-switched envelope is estimated to be about 200 ps.     

A comment on the theory of one-dimensional mixing-frequency electron spin echo envelope modulation (MIF-ESEEM) spectroscopy

The theory of one-dimensional mixing-frequency electron-spin-echo envelope modulation (MIF-ESEEM) spectroscopy of disordered systems has been revised. In particular, the correct dependence of the position and width of the MIF-ESEEM peaks on the experimental parameters has been obtained, thus providing formulas which enable one to properly interpret the experimental data. The differences with the previously published analyses are discussed. The close relationship with the two-dimensional HYSCORE spectroscopy is remarked on. Experimental examples demostrate the main results.     

High power diode-pumped passively Q-switched and mode-locking Nd:GdVO4 laser at 912 nm

A high power diode-end-pumped passively Q-switched and mode-locking (QML) Nd:GdVO₄ laser at 912 nm was demonstrated for the first time, to the best of our knowledge. A Z-type laser cavity with Cr⁴⁺:YAG crystals as the intracavity saturable absorber were employed in the experiments. Influence of the initial transmission (T_U) of the saturable absorber on the QML laser performance was investigated. Using the T_U = 95% Cr⁴⁺:YAG, as much as an average output power of 2.0 W pulsed 912 nm laser was produced at an absorbed pump power of 25.0 W, then the repetition rates of the Q-switched envelope and the mode-locking pulse were ~ 224 kHz and ~ 160 MHz, respectively. Whereas the maximum output power was reduced to 1.3 W using the T_U = 90% Cr⁴⁺:YAG, we obtained a 100% modulation depth for the mode-locking pulses inside the Q-switched envelope.     

ERD studies of D-ion depth distributions after implantation into some pure metals and alloys

This paper presents a report on experimental results of depth distributions of deuterium ions implanted with 25 keV energy at a fluence interval of (1.2–2.3) × 10²² m⁻² into samples of pure metals (Cu, Ti, Zr, V, Pd) and diluted Pd alloys (Pd-Ag, Pd-Pt, Pd-Ru, Pd-Rh). The post-treatment depth distributions of deuterium and hydrogen atoms were measured within a few hours after implantation with the use of elastic recoil detection (ERD) analysis. After three months the measurements were repeated. The comparison of the obtained results in both series of studies allowed us to make an important observation of the desorption rates of implanted deuterium atoms from pure metals and diluted Pd alloys. The maximum measured concentrations of deuterium atoms in pure Zr and Ti foils with relatively small desorption rate of deuterium atoms within three months after implantation were observed. Also a very high spreading of deuterium atom distributions was observed in all the measured pure metals and alloys. It can be explained by the large diffusion coefficients of deuterium and extremely fast kinetics.     

Analysis of a laser-diode end-pumped intracavity frequency-doubled passively Q-switched and mode-locked Nd:GdVO<Subscript>4</Subscript>/KTP laser with a semiconductor saturable absorber

A diode-pumped passively Q-switched mode-locked (QML) intracavity frequency-doubled Nd:GdVO₄/KTP green laser with a semiconductor saturable absorber is presented. Nearly 100% modulation depth for the mode-locked green pulses can be achieved at any pump power over 1.92 W. The width of the mode-locked green pulse was estimated to be about 150 ps. The mode-locked pulse interval within the Q-switched envelope of 320 ns and the repetition rate of 97.5 kHz were obtained, at an incident pump power of 4.4 W. The repetition rate of the mode-locked green pulses inside the Q-switched envelope was 140 MHz.     

Observation of potassium hyperfine interactions in x-irradiated KH2AsO4 through the method of electron spin echo envelope modulation

Hyperfine interaction frequencies of ¹H and ³⁹K nuclei near the AsO^4-₄ radical in X-ray irradiated KH₂AsO₄ (KDA) have been observed through the method of electron spin echo envelope modulation (ESEEM). This method enabled us to record nuclear hyperfine interaction (ENDOR-like) spectra around the ferroelectric phase transition of KDA for the first time. The ESEEM spectrum of ³⁹K exhibits a clear change when passing the ferroelectric phase transition temperature, but that of close protons does not. The result for close protons is in agreement with the symmetry breaking of the AsO^4-₄ site as observed via the EPR spectrum [5]. Finally, at 4.2 K the hyperfine interaction parameters of a ³⁹K nucleus near the AsO^4-₄ unit could be determined through the ESEEM method.     

Microwave spectroscopic study of the CO-H2S complex

Rotational spectra of the CO-H₂S complex were studied using a cavity Fourier transform microwave spectrometer. Altogether 16 isotopomers were investigated. The tunneling splitting due to interchange of the “bonded” and “non-bonded” hydrogen (deuterium) nuclei of the H₂S (D₂S) subunit was observed and analyzed. In addition, the nuclear quadrupole hyperfine structures due to the quadrupolar ³³S and ¹⁷O nuclei could be resolved and analyzed. The resulting rotational, tunneling, and hyperfine constants were used to derive structural and dynamical information about the complex.     

Diffusion of deuterium in tantalum from internal friction measurements (Gorsky effect)

The long-range diffusion of deuterium in tantalum has been investigated as a function of temperature by means of the anelastic process due to redistribution of deuterium impurities between compressed and dilated regions of the sample, under an applied stress alternating at about 4 Hz. The diffusion coefficient was found to obey an Arrhenius-type law in the temperature range 200–390 K; a deviation was observed at lower temperatures. The diffusion parameters in the exponential region areD _0D=(3.3±1.5)×10⁻⁴ cm²/s, andW _D=(0.176±0.008) eV.     

Electrically detected electron-spin-echo envelope modulation: a highly sensitive technique for resolving complex interface structures

We show that the electrical detection of electron-spin-echo envelope modulation (ESEEM) is a highly sensitive tool to study interfaces. Taking the Si/SiO2 interface defects in phosphorus-doped crystalline silicon as an example, we find that the main features of the observed echo modulation pattern allow us to develop a microscopic model for the dangling-bond-like P(b0) center by comparison with the results of ab initio calculations. The ESEEM spectrum is found to be far more sensitive to the defect characteristics than the spectrally resolved hyperfine splitting itself.