Study of Stable L-Alanine Radicals by W-Band EPR Spectroscopy

Stable L-alanine radicals, SAR1 and SAR2, induced by γ-irradiation of the L-alanine crystal have been investigated by electron paramagnetic resonance (EPR) technique at W-band (94 GHz) frequency. The study provides assignment of radical centers detected by continuous-wave EPR, saturation transfer mode and echo-detected field-swept EPR at W-band frequencies. The phase memory time, T _m, which was measured simultaneously at X-band (9.5 GHz) and W-band frequencies for different spectral components has been employed to estimate rotation correlation times of CH₃ protons and an effective correlation time related to the local dynamics of the entire SAR1 center at room temperature.     

A Rapid Calibration Technique for Scanning Line-Structured Laser Sensor

A novel procedure to calibrate the scanning line-structured laser sensor is presented. A drone composed of two orthogonal planes is designed, with the result that camera parameters and light-plane equation parameters is achieved simultaneously.     

Rapid frequency scan EPR

In rapid frequency scan EPR with triangular scans, sufficient time must be allowed to insure that the magnetization in the x, y plane decays to baseline at the end of the scan, which typically is about 5T(2) after the spins are excited. To permit relaxation of signals excited toward the extremes of the scan the total scan time required may be much longer than 5T(2). However, with periodic, saw-tooth excitation, the slow-scan EPR spectrum can be recovered by Fourier deconvolution of data recorded with a total scan period of 5T(2), even if some spins are excited later in the scan. This scan time is similar to polyphase excitation methods. The peak power required for either polyphase excitation or rapid frequency scans is substantially smaller than for pulsed EPR. The use of an arbitrary waveform generator (AWG) and cross loop resonator facilitated implementation of the rapid frequency scan experiments reported here. The use of constant continuous low B(1), periodic excitation waveform, and constant external magnetic field is similar to polyphase excitation, but could be implemented without the AWG that is required for polyphase excitation.     

A W-Band Frequency Tracing Transceiver System

In millimeter-wave, phase-locked oscillators are often used because the frequency drift of oscillators is very large. However, they are very complex. In this paper, a W-band frequency tracing transceiver system is presented and tested, which is used for digital communication. Although the communication distance is less than that of phase-locked systems, the scheme is simple and the cost is low.     

Design,Implementation, Simulation,and Visualization of a Highly Efficient RIM Microfluidic Mixer for Rapid Freeze-Quench of Biological Samples

Abstract  

Rapid freeze-quench (RFQ) trapping of short-lived reaction intermediates for spectroscopic study plays an important role in the characterization of biological reactions. Recently, there has been considerable effort to achieve sub-millisecond reaction deadtimes. We present here a new, robust, high-velocity microfluidic mixer that enables such rapid freeze-quenching. It is a based on the mixing method of two impinging jets commonly used in reaction injection molding of plastics. This method achieves efficient mixing by inducing chaotic flow at relatively low Reynolds numbers (Re = 140). We present the first mathematical simulation and microscopic visualization of mixing in such RFQ micromixers, the results of which show that the impinging solutions efficiently mix within the mixing chamber. These tests, along with a practical demonstration in an RFQ setup that involves copper wheels, show that this new mixer can in practice provide reaction deadtimes as low as 100 μs.     

多元校正结合质谱数据进行四种有机物快速含量分析研究

质谱法和化学计量学方法相结合对混合物中苯甲醛,异辛烷,乙酸丁酯,苯乙酮四种物质进行定量分析。将混合物的质量色谱图数据分别用特征选择-多元线性回归（MLR）和全谱-偏最小二乘法（PLS）这两种方法对四种物质进行定量分析。苯甲醛特征选择和全谱建模的RMSEP分别为0.062和0.091; 异辛烷特征选择和全谱建模的RMSEP分别为0.048和0.057; 乙酸丁酯特征选择和全谱建模的RMSEP分别为0.021和0.020; 苯乙酮特征选择和全谱建模的RMSEP分别为0.010和0.032。结果表明苯甲醛,异辛烷,苯乙酮特征选择的结果均优于全谱建模的结果,乙酸丁酯特征选择的结果和全谱建模的结果相近。     

Dielectric Resonator-Based Flow and Stopped-Flow EPR with Rapid Field Scanning: A Methodology for Increasing Kinetic Information

We report methodology which combines recently developed dielectric resonator-based, rapid-mix, stopped-flow EPR (appropriate for small, aqueous, lossy samples) with rapid scanning of the external (Zeeman) magnetic field where the scanning is preprogrammed to occur at selected times after the start of flow. This methodology gave spectroscopic information complementary to that obtained by stopped-flow EPR at single fields, and with low reactant usage, it yielded more graphic insight into the time evolution of radical and spin-labeled species. We first used the ascorbyl radical as a test system where rapid scans triggered after flow was stopped provided “snapshots” of simultaneously evolving and interacting radical species. We monitored ascorbyl radical populations either as brought on by biologically damaging peroxynitrite oxidant or as chemically and kinetically interacting with a spectroscopically overlapping nitroxide radical. In a different biophysical application, where a spin-label lineshape reflected rapidly changing molecular dynamics of folding spin-labeled protein, rapid scan spectra were taken during flow with different flow rates and correspondingly different times after the mixing-induced inception of protein folding. This flow/rapid scan method is a means for monitoring early immobilization of the spin probe in the course of the folding process.     

A program for simulation of powder-type EPR spectra

An algorithm of a computer program for simulation of powder type EPR spectra (S=1/2,I≠0) is described. For determination of the energy levels, the perturbation approach is used and corrections up to second order due to hyperfine, quadrupole, and nuclear Zeeman coupling are taken into account. No restrictions on the mutual orientations of the eigenvectors ofg, hyperfine, and quadrupole tensors are imposed. Simulated spectra for a model paramagnetic system (S=1/2,I=3/2) with axial symmetry and noncoinciding directions ofg _‖ andA _‖ are presented.     

A Fixed-Tuned W-Band Waveguide SIS Mixer with 4.0-7.5 GHz IF

The design and performance of a fixed-tuned W-band SIS mixer with a wide band IF of 4.0-7.5 GHz is presented. Waveguide-to-stripline transition of the SIS mixer is designed using the lumped-gap-source port provided by HFSS^TM. Measured receiver noise temperature is less than 25 K in the frequency range of 95-120 GHz, with a minimum value of around 19 K achieved. Mixer noise temperature is determined to be about 8.5 K, which is around twice the quantum limit (i.e., 2hw/k). In spite of the high IF frequencies (f ₀ = 6 GHz), the performance of the SIS receiver is comparable or even superior to those of the best mechanically-tunable waveguide SIS receivers at low IF frequencies (f ₀ = 1.5 GHz). This result suggests that it is easy to design waveguide-to-stripline transitions without scale-model measurements.     

A statistical theory for powder EPR in distributed systems

A statistical interpretation is presented for “g strain,” the dominant broadening in the EPR spectra of metallo-proteins. The direct cause of g strain is described by a three-dimensional tensor p, whose principal elements are random variables. The p and g tensors are not necessarily colinear. The observed EPR linewidth results from a distribution in the effective g value as a function of (a) the joint distribution function of the elements of the p tensor and (b) the spatial relationship between the two principal axis systems involved. The theory is reformulated in terms of matrices that facilitate a direct comparison with earlier work. Two previous theories of g strain represent different subsets of the general theory, namely, the case of zero rotation between axis systems and the case with nonzero rotation and full correlation between elements of the p tensor.     

A virtually nondestructive EPR technique accounting for diagnostic X-rays

We have implemented the method proposed by Aldrich and Pass (Aldrich, J.E., Pass, B., 1988. Determining radiation exposure from nuclear accidents and atomic tests using dental enamel. Health Phys. 54, 469–471.) to measure both the interior and exterior portions of a tooth in order to determine the diagnostic X-ray component of the total dose in the teeth. This was done using a modified nondestructive approach of Haskell et al. (Haskell, E.H., Hayes, R.B., Romanyukha, A.A., Kenner, G.H., 2000. Preliminary report on the development of a virtually non-destructive additive dose technique for EPR dosimetry Appl. Radiat Isot. 52, 1065–1070.) given in Hayes et al. ( Hayes, R.B., Haskell, E.H., Barrus, J.K., Kenner, G.H., Romanyukha, A.A., 2000. Accurate EPR radiosensitivity calibration using small sample masses. Nucl. Instr. Meth. A. 441, 535–550). Here only 5% of the total tooth enamel sample from an enamel crown was used for individual sample sensitivity calibration. A cavity response correction for the low mass samples was also used ( Hayes et al., 2000). The teeth were American wisdom teeth having unknown doses applied by the IAEA in the range of 0 to 1 Gy as part of the second international intercomparison ( Wieser, A., Mehta, K., Amira, S., Aragno, S., Bercea, S., Brik, A., Bugai, A., Callens, F., Chumak, V., Ciesielski, B., Debuyst, R., Dubovsky, S., Duliu, O., Fattibene, P., Haskell, E., Hayes, R., Ignatiev, E., Ivannikov, A., Kirillov, V., Kleschenko, E., Nakamura, N., Nathe, M., Nowak, J., Onori, S., Pass, B., Pivovarov, S., Romanyukha, A., Scherbina, O., Shames, A., Sholom, S., Skvortsov, V., Stepanenko, V., Tikounov, D., Toyoda, S., 2000. The 2nd international intercomparison on EPR tooth dosimetry. Radiat. Meas. in press). Final dose reconstruction estimates of the IAEA applied values showed a very high correlation (R=0.996). The approximate excess dose measured on the outside of the teeth relative to the inside was 49±35 mGy which is attributed to the diagnostic X-ray exposure given to the America wisdom teeth prior to extraction. The method used showed only a small dependence on the accelerating voltage of the X-ray source.     

一种EPR谱图模拟软件的研制

采用Microsoft Visual BASIC 4.0 for Windows 95编写了一个EPR谱图模拟软件.此软件采用鼠标控制命令按键进行程序过程.得到的图象分辨率和色彩优于用其他早期开发的BASIC语言编写的程序,打印的黑白图象质量也很好.运算时间小于20秒.这种软件可用于多种EPR模拟应用,包括自由基EPR谱图的模拟、过渡金属离子E PR谱图的模拟和二维EPR成像的模拟.EPR成像可以彩色强度图、等高线图或三维俯视图来表示.所有的模拟图象均可用激光打印机打印成黑白图片.自由基模拟程序的数据组有2560点.EPR成像的像素一般为128×128点.     

Mössbauer and EPR Study of Reaction Intermediates of Cytochrome P450

Hyperfine Interactions - We present a complementary Mössbauer and EPR study on reaction intermediates of substrate-free and substrate-bound cytochrome P450cam from Pseudomonas putida prepared...     

Millimeter wave pulsed gunn oscillator for low chirp radar application at W-Band

Pulsed Gunn oscillator at 94 GHz has been developed using GaAs CW Gunn diode, by choosing a proper operating point and resonant circuit. Peak power output of 25 mw at 94 GHz with a pulse width of 2 microseconds and duty factor of 2% is achieved. Bias circuit oscillations are suppressed by rising the operating voltage alongwith other circuit considerations.     

A method for enhancing the resolution of overlapping EPR lines

A simple and fast method for enhancing the resolution of overlapping EPR lines based on the convolution theorem of Fourier analysis is presented. The method provides two analytic expressions in real space by means of which the user can remove, by deconvolution, either a Lorentzian or a Gaussian function from a given experimental spectrum. This method is applied to deconvolve the line-overlapping EPR spectrum of molybdenumphthalocyanine (MoPc) in solution in fuming sulfuric acid. The deconvolved spectrum is then compared with the EPR spectrum of MoPc incorporated in concentrated sulfuric acid where the lines do not extensively overlap. Comparison shows that the method is able to enhance the resolution of the originally masked hyperfine pattern of MoPc in the fuming sulfuric acid spectrum. This method can be easily applied to other spectroscopies.     

A Local Realistic Theory for Mermin’s EPR Experiment

As another counterexample to prevalent conventional belief, a realistic theory, which is local and reproduces all the probabilistic predictions of quantum theory, is presented for Mermin’s version of the Einstein-Podolsky-Rosen (EPR) experiment.     

EPR and ENDOR Investigation of Rhodosemiquinone in Bacterial Reaction Centers Formed by B-Branch Electron Transfer

In photosynthetic bacteria, light-induced electron transfer takes place in a protein called the reaction center (RC) leading to the reduction of a bound ubiquinone molecule, Q_B, coupled with proton binding from solution. We used electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) to study the magnetic properties of the protonated semiquinone, an intermediate proposed to play a role in proton coupled electron transfer to Q_B. To stabilize the protonated semiquinone state, we used a ubiquinone derivative, rhodoquinone, which as a semiquinone is more easily protonated than ubisemiquinone. To reduce this low-potential quinone we used mutant RCs modified to directly reduce the quinone in the Q_B site via B-branch electron transfer (Paddock et al. in Biochemistry 44:6920–6928, 2005). EPR and ENDOR signals were observed upon illumination of mutant RCs in the presence of rhodoquinone. The EPR signals had g values characteristic of rhodosemiquinone (g _x  = 2.0057, g _y  = 2.0048, g _z  ~ 2.0018) at pH 9.5 and were changed at pH 4.5. The ENDOR spectrum showed couplings due to solvent exchangeable protons typical of hydrogen bonds similar to, but different from, those found for ubisemiquinone. This approach should be useful in future magnetic resonance studies of the protonated semiquinone.