Two-Dimensional Pulsed TRIPLE at 95 GHz

The one-dimensional (1D) pulsed TRIPLE resonance experiment, introduced by Mehring et al. (M. Mehring, P. Höfer, and A. Grupp, Ber. Bunseges. Phys. Chem. 91, 1132-1137 (1987)) is a modification of the standard Davies ENDOR experiment where an additional RF π-pulse is applied during the mixing time. While the first RF pulse is set to one of the ENDOR transitions, the frequency of the second RF pulse is scanned to generate the TRIPLE spectrum. The difference between this spectrum and the ENDOR spectrum yields the difference TRIPLE spectrum, which exhibits only ENDOR lines that belong to the same Ms manifold as the one selected by the first RF pulse. We have extended this experiment in two dimensions (2D) by sweeping the frequencies of both RF pulses. This experiment is particularly useful when the spectrum is congested and consists of signals originating from different paramagnetic centers. The connectivities between the peaks in the 2D spectrum enable a straightforward assignment of the signals to their respective centers and Ms manifolds, thus providing the relative signs of hyperfine couplings. Carrying out the experiment at high fields has the additional advantage that nuclei with different nuclear gyromagnetic ratios are well separated. This is particularly true for protons which appear at significantly higher frequencies than other nuclei. The feasibility and effectiveness of the experiment is demonstrated at W-band (94.9 GHz) on a crystal of Cu2+-doped L-histidine. Homonuclear 1H-1H, 14N/35Cl-14N/35Cl and heteronuclear 1H-14N/35Cl 2D TRIPLE spectra were measured and from the various connectivities in the 2D map the 1H, 14N, and 35Cl signals that belong to two different Cu2+ centers were identified and grouped according to their Ms manifolds. © 2000 Academic Press

An AC susceptometer for the characterization of large, bulk superconducting samples

The main purpose of this work was to design, develop and construct a simple, low-cost AC susceptometer to measure large, bulk superconducting samples (up to 32 mm in diameter) in the temperature range 78-120 K. The design incorporates a double heating system that enables a high heating rate (25 K/hour) while maintaining a small temperature gradient (< 0.2 K) across the sample. The apparatus can be calibrated precisely using a copper coil connected in series with the primary coil. The system has been used successfully to measure the temperature dependence of the AC magnetic properties of entire RE-Ba-Cu-O [(RE)BCO] bulk superconducting domains. A typical AC susceptibility measurement run from 78 K to 95 K takes about 2 hours, with excellent temperature resolution (temperature step ~ 4 mK) around the critical temperature, in particular.Comment: 25 pages, 7 figures. Accepted for publication in Measurement Science and Technolog

RIDME distance measurements using Gd(iii) tags with a narrow central transition

Methods based on pulse electron paramagnetic resonance allow measurement of the electron-electron dipolar coupling between two spin labels. Here we compare the most popular technique, Double Electron-Electron Resonance (DEER or PELDOR), with the dead-time free 5-pulse Relaxation-Induced Dipolar Modulation Enhancement (RIDME) method for Gd(iii)-Gd(iii) distance measurements at W-band (94.9 GHz, ≈3.5 T) using Gd(iii) tags with a small zero field splitting (ZFS). Such tags are important because of their high EPR sensitivity arising from their narrow central transition. Two systems were investigated: (i) a rigid model compound with an inter-spin distance of 2.35 nm, and (ii) two mutants of a homodimeric protein, both labeled with a DOTA-based Gd(iii) chelate and characterized by an inter-spin distance of around 6 nm, one having a narrow distance distribution and the other a broad distribution. Measurements on the model compound show that RIDME is less sensitive to the complications arising from the failure of the weak coupling approximation which affect DEER measurements on systems characterized by short inter-spin distances between Gd(iii) tags having a narrow central transition. Measurements on the protein samples, which are characterized by a long inter-spin distance, emphasize the complications due to the appearance of harmonics of the dipolar interaction frequency in the RIDME traces for S > 1/2 spin systems, as well as enhanced uncertainties in the background subtraction. In both cases the sensitivity of RIDME was found to be significantly better than DEER. The effects of the experimental parameters on the RIDME trace are discussed.This research was supported by the Israeli Science Foundation (grant 334/14) and was made possible in part by the historic generosity of the Harold Perlman Family (D. G.). We also acknowledge the Australian Research Council for a Discovery grant to G. O. and B. G. (DP150100383) and a Future Fellowship to B. G. (FT130100838). D. G. holds the Erich Klieger professorial chair in Chemical Physics

A Quadratic Programming Approach to Quasi-Static Whole-Body Manipulation

This paper introduces a local motion planning method for robotic systems with manipulating limbs, moving bases (legged or wheeled), and stance stability constraints arising from the presence of gravity. We formulate the problem of selecting local motions as a linearly constrained quadratic program (QP), that can be solved efficiently. The solution to this QP is a tuple of locally optimal joint velocities. By using these velocities to step towards a goal, both a path and an inverse-kinematic solution to the goal are obtained. This formulation can be used directly for real-time control, or as a local motion planner to connect waypoints. This method is particularly useful for high-degree-of-freedom mobile robotic systems, as the QP solution scales well with the number of joints. We also show how a number of practically important geometric constraints (collision avoidance, mechanism self-collision avoidance, gaze direction, etc.) can be readily incorporated into either the constraint or objective parts of the formulation. Additionally, motion of the base, a particular joint, or a particular link can be encouraged/discouraged as desired. We summarize the important kinematic variables of the formulation, including the stance Jacobian, the reach Jacobian, and a center of mass Jacobian. The method is easily extended to provide sparse solutions, where the fewest number of joints are moved, by iteration using Tibshirani’s method to accommodate an l_1 regularizer. The approach is validated and demonstrated on SURROGATE, a mobile robot with a TALON base, a 7 DOF serial-revolute torso, and two 7 DOF modular arms developed at JPL/Caltech

Rooting Cuttings of Northern Red Oak (Quercus rubra L.)

Several techniques have been used experimentally to vegetatively propagate northern red oak (Quercus rubra L.), including: 1) rooting juvenile softwood cuttings in intermittent mist, 2) rooting shoots originating from mature buds grafted onto juvenile root stocks, and 3) in vitro shoot proliferation of juvenile or mature shoots followed by in vitro rooting. Of these techniques, rooting juvenile softwood cuttings has provided the most consistent results for northern red oak (NRO). Juvenility (or at least the associated ability to form adventitious roots) disappears rapidly among progressive flushes of growth in NRO seedlings. Decreased rooting has been reported for NRO shoots obtained from progressive flushes of growth produced within a growing season, as well as shoots representing flushes obtained from successive seasons of growth. However, as with many other tree species, the process of maturation in NRO can be slowed by pruning to encourage juvenile shoot production. Optimizing the number of juvenile cuttings produced from each stock plant is necessary for efficient rooted cutting production systems. In addition, rooting conditions must be determined for the shoots produced under these pruning regimes. Two NRO rooted cutting studies are currently being conducted at NCSU. The objective of the first study is to evaluate the effects of stock plant pruning location, diameter, and age on new shoot production. Treatments include pruning first-year seedlings, as well as one-, two-, and three-year-old seedlings to the base of the first, second, third, or fourth flush of growth produced during the first growing season. The objective of the second study is to evaluate the ability of the shoots produced in the first study to form adventitious roots. Treatments include three rooting hormone levels (0.5%, 1%, and 1.5% IBA) and a control (45% EtOH). Preliminary results from both studies will be presented.Papers and abstracts from the 27th Southern Forest Tree Improvement Conference held at Oklahoma State University in Stillwater, Oklahoma on June 24-27, 2003

Protein conformation by EPR spectroscopy using gadolinium tags clicked to genetically encoded p-azido-L-phenylalanine

Quantitative cysteine-independent ligation of a Gd(3+) tag to genetically encoded p-azido-L-phenylalanine via Cu(I)-catalyzed click chemistry is shown to deliver an exceptionally powerful tool for Gd(3+)-Gd(3+) distance measurements by double electron-electron resonance (DEER) experiments, as the position of the Gd(3+) ion relative to the protein can be predicted with high accuracy.This work was supported by the Australian Research Council (ARC), an Australia-Weizmann Making Connections grant, and the Israel Science Foundation (ISF)

On the ultimate convergence rates for isotropic algorithms and the best choices among various forms of isotropy

In this paper, we show universal lower bounds for isotropic algorithms, that hold for any algorithm such that each new point is the sum of one already visited p oint plus one random isotropic direction multiplied by any step size (whenever the step size is chosen by an oracle with arbitrarily high computational power). The bound is 1 − O(1/d) for the constant in the linear convergence (i.e. the constant C such that the distance to the optimum after n steps is upp er b ounded by C n ), as already seen for some families of evolution strategies in [19, 12], in contrast with 1 − O(1) for the reverse case of a random step size and a direction chosen by an oracle with arbitrary high computational power. We then recall that isotropy does not uniquely determine the distribution of a sample on the sphere and show that the convergence rate in isotropic algorithms is improved by using stratified or antithetic isotropy instead of naive isotropy. We show at the end of the pap er that b eyond the mathematical proof, the result holds on exp eriments. We conclude that one should use antithetic-isotropy or stratified-isotropy, and never standard-isotropy

Online Display Advertising: Targeting and Intrusiveness

We use data from a large-scale field experiment to explore what influences the effectiveness of online advertising. We find that matching an ad to website content and increasing an ad's obtrusiveness independently increase purchase intent. However, in combination, these two strategies are ineffective. Ads that match both website content and are obtrusive do worse at increasing purchase intent than ads that do only one or the other. This failure appears to be related to privacy concerns: the negative effect of combining targeting with obtrusiveness is strongest for people who refuse to give their income and for categories where privacy matters most. Our results suggest a possible explanation for the growing bifurcation in Internet advertising between highly targeted plain text ads and more visually striking but less targeted ads

Spectrometer manager: A versatile control software for pulse EPR spectrometers

A versatile control software for pulse EPR spectrometers is introduced. Common and task-specific problems are discussed and their solutions are described. The software provides the full spectrum of possibilities needed to perform arbitrary multidimensional pulse experiments. It allows for an easy interfacing of commonly used hardware components and enables straightforward modifications of the spectrometer. Good performance, configurability, and a number of unique features turn this software into an excellent tool for the operation of modern EPR spectrometers and upgrading old ones. © 2005 Wiley Periodicals, Inc

Multipurpose High Frequency Electron Spin Resonance Spectrometer for Condensed Matter Research

We describe a quasi-optical multifrequency ESR spectrometer operating in the 75-225 GHz range and optimized at 210 GHz for general use in condensed matter physics, chemistry and biology. The quasi-optical bridge detects the change of mm wave polarization at the ESR. A controllable reference arm maintains a mm wave bias at the detector. The attained sensitivity of 2x10^10 spin/G/(Hz)1/2, measured on a dilute Mn:MgO sample in a non-resonant probe head at 222.4 GHz and 300 K, is comparable to commercial high sensitive X band spectrometers. The spectrometer has a Fabry-Perot resonator based probe head to measure aqueous solutions, and a probe head to measure magnetic field angular dependence of single crystals. The spectrometer is robust and easy to use and may be operated by undergraduate students. Its performance is demonstrated by examples from various fields of condensed matter physics.Comment: submitted to Journal of Magnetic Resonanc