A high-spin ground-state donor-acceptor conjugated polymer.

Interest in high-spin organic materials is driven by opportunities to enable far-reaching fundamental science and develop technologies that integrate light element spin, magnetic, and quantum functionalities. Although extensively studied, the intrinsic instability of these materials complicates synthesis and precludes an understanding of how fundamental properties associated with the nature of the chemical bond and electron pairing in organic materials systems manifest in practical applications. Here, we demonstrate a conjugated polymer semiconductor, based on alternating cyclopentadithiophene and thiadiazoloquinoxaline units, that is a ground-state triplet in its neutral form. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-to-low spin energy gap of 9.30 × 10-3 kcal mol-1. The strongly correlated electronic structure, very narrow bandgap, intramolecular ferromagnetic coupling, high electrical conductivity, solution processability, and robust stability open access to a broad variety of technologically relevant applications once thought of as beyond the current scope of organic semiconductors.

Imaging considerations for in vivo 13C metabolic mapping using hyperpolarized 13C-pyruvate.

One of the challenges of optimizing signal-to-noise ratio (SNR) and image quality in (13)C metabolic imaging using hyperpolarized (13)C-pyruvate is associated with the different MR signal time-courses for pyruvate and its metabolic products, lactate and alanine. The impact of the acquisition time window, variation of flip angles, and order of phase encoding on SNR and image quality were evaluated in mathematical simulations and rat experiments, based on multishot fast chemical shift imaging (CSI) and three-dimensional echo-planar spectroscopic imaging (3DEPSI) sequences. The image timing was set to coincide with the peak production of lactate. The strategy of combining variable flip angles and centric phase encoding (cPE) improved image quality while retaining good SNR. In addition, two aspects of EPSI sampling strategies were explored: waveform design (flyback vs. symmetric EPSI) and spectral bandwidth (BW = 500 Hz vs. 267 Hz). Both symmetric EPSI and reduced BW trended toward increased SNR. The imaging strategies reported here can serve as guidance to other multishot spectroscopic imaging protocols for (13)C metabolic imaging applications.

Detection of Anoplophora glabripennis (Coleoptera: Cerambycidae) larvae in different host trees and tissues by automated analyses of sound-impulse frequency and temporal patterns.

Anoplophora glabripennis (Motschulsky) (Coleoptera: Cerambycidae), an invasive pest quarantined in the United States, is difficult to detect because the larvae feed unseen inside trees. Acoustic technology has potential for reducing costs and hazards of tree inspection, but development of practical methods for acoustic detection requires the solution of technical problems involving transmission of resonant frequencies in wood and high background noise levels in the urban environments where most infestations have occurred. A study was conducted to characterize sounds from larvae of different ages in cambium, sapwood, and heartwood of bolts from three host tree species. Larval sounds in all of the tested trees and tissues consisted primarily of trains of brief, 3-10-ms impulses. There were no major differences in the spectral or temporal pattern characteristics of signals produced by larvae of different ages in each tissue, but larval sounds in sapwood often had fewer spectral peaks than sounds in cambium and heartwood. A large fraction, but not all background sounds could be discriminated from larval sounds by automated spectral analyses. In 3-min recordings from infested bolts, trains containing impulses in patterns called bursts occurred frequently, featuring 7-49 impulses separated by small intervals. Bursts were rarely detected in uninfested bolts. The occurrence of bursts was found to predict infestations more accurately than previously used automated spectral analyses alone. Bursts and other features of sounds that are identifiable by automated techniques may ultimately lead to improved pest detection applications and new insight into pest behavior.

In vivo 13 carbon metabolic imaging at 3T with hyperpolarized 13C-1-pyruvate.

We present for the first time dynamic spectra and spectroscopic images acquired in normal rats at 3T following the injection of (13)C-1-pyruvate that was hyperpolarized by the dynamic nuclear polarization (DNP) method. Spectroscopic sampling was optimized for signal-to-noise ratio (SNR) and for spectral resolution of (13)C-1-pyruvate and its metabolic products (13)C-1-alanine, (13)C-1-lactate, and (13)C-bicarbonate. Dynamic spectra in rats were collected with a temporal resolution of 3 s from a 90-mm axial slab using a dual (1)H-(13)C quadrature birdcage coil to observe the combined effects of metabolism, flow, and T(1) relaxation. In separate experiments, spectroscopic imaging data were obtained during a 17-s acquisition of a 20-mm axial slice centered on the rat kidney region to provide information on the spatial distribution of the metabolites. Conversion of pyruvate to lactate, alanine, and bicarbonate occurred within a minute of injection. Alanine was observed primarily in skeletal muscle and liver, while pyruvate, lactate, and bicarbonate concentrations were relatively high in the vasculature and kidneys. In contrast to earlier work at 1.5 T, bicarbonate was routinely observed in skeletal muscle as well as the kidney and vasculature.

Effects of mild food deprivation on the estrous cycle of rats.

It has long been known that severe food deprivation disrupts the estrous cycle. One of the main problems with behavioral tasks that use food for reinforcement is the requirement that the animal be food deprived. This manipulation could be problematic in studies using female animals, since it may interfere with the estrous cycle of the animals. The purpose of the present study was to investigate: (1) the effect of mild food deprivation on four different strains of rats, (2) factors in the food deprivation procedure that could affect the estrous cycle, and (3) the possible effect of enriched diets during food deprivation on the estrous cycle. A comparison of the estrous cycle in four different rat strains revealed differences in the reliability of the estrous cycle even before the onset of food deprivation. Fischer, Long-Evans, and Sprague-Dawley rats all showed reliable cycle patterns. This was not the case for Brown Norway rats. During food deprivation, the cycle of the Fischer rats was disrupted, whereas the Long-Evans and Sprague-Dawley animals continued to cycle. Both the rate of weight loss and the percent of ad libitum body weight were related to cessation of the estrous cycle. However, enriching an animal's diet with sugar or oil additives delayed the disruption of the estrous cycle. Additionally, animals resumed cycling when returned to ad libitum weight levels. The present findings suggest that when animals need to be food deprived, preference should be given to using Long-Evans or Sprague-Dawley rats. If Fischer rats must be used, they should not be deprived below 90-95% of their ad libitum body weight. Strategies for future food deprivation studies are discussed, as well as a comparison of the effects of mild and severe food deprivation.

Spatial dependence of a differential shading artifact in images from coil arrays with reactive cross-talk at 1.5 T.

Reactive cross-talk causes leakage of the reception signal between neighboring coils of a receiver array. We present here experimental and computer-simulated NMR images (based upon a simple theory) to show, for an array of two coils, that the leakage (or secondary) signal is combined phase sensitively with the primary signal in each coil, to produce (in certain geometries) a differential shading artifact, manifest as a divot of missing intensity in the image derived from one (and only one) of the two coils. The asymmetry of this effect arises from the sense of the nuclear precession, and the afflicted coil may be swapped with its mate by reversing the direction of the static magnetic field. The artifact appears most clearly in transaxial images and is shown to be forbidden in certain types of saggital images. In a simplified theory for an array of two meshes (i.e., with only two degrees of freedom) the severity of the artifact depends upon the normalized coefficient of coupling (denoted eta and related to the cross-talk in decibels, psi, by psi=-20 log eta.) While the presence of input trap circuits in a typical array doubles the degrees of freedom and complicates both the circuit theory and the circuit measurements, the cross-talk is nonetheless shown to be given by an expression of the form psi=-20 log eta', where the new primed parameter eta' embodies the impedance-matching capacitance and the resistance of the scanner's preamplifiers, as well as the mutual reactance responsible for the cross-talk. The values of cross-talk inferred from the computer simulations of the image artifact are somewhat higher (by an estimated 3 to 6 dB) than those obtained by bench top measurements; but, given that the simulations unmistakably reproduce the unique and highly characteristic visual appearance of the artifact, the proposed model for its formation is claimed to be essentially correct. Finally, it is suggested that the artifact could be corrected by means of the filtered, edge-completed, reception profile described by Wald and co-workers (Wald et al., Magn. Reson. Med. 34, 433 (1995)).

Sex differences in the dynamics of cue utilization and exploratory behavior.

The purpose of the present study was to investigate the effects of sex and estrous cycle on exploratory behavior, as well as the degree to which reliance on environmental cues changes with training. Fischer 344 rats were placed three times in an open field box that contained three objects (two identical bottles and a cylinder). During the initial exposure to the environment all females showed higher activity levels and explored a larger region of the environment compared to males. However, upon subsequent exposure to the same environment, these sex differences disappeared. During the third and final session, the locations of the bottle and the cylinder were switched. The estrous females and to a lesser degree male rats, responded to the relocation of objects with a renewal of exploration and activity; proestrous females did not show this response. The rats were then trained on a four-arm radial maze reference memory task. The correct arm could be located by its relation to extra-room cues, a large distal white panel, or to local inserts on the maze. Once the animals consistently chose the goal arm, a probe session was conducted to determine which cues the animals were using to solve the task. During the probe trial both the white panel and the local inserts were rotated 90 degrees clockwise and counterclockwise respectively and the animals' choice of arm recorded. During the first probe, females tended to rely on all three types of cues in solving the task. With additional training there was a shift towards predominantly using the distal visual information. In contrast, male rats did not show this shift; by the first probe session the males were predominantly using the distal visual information to solve the task. The findings indicate: (1) sex differences in the initial use of environmental cues; (2) the usage of environmental information is dynamic and changes with additional exposures to the environment. The results are related to previous findings on sex differences and estrous cycle effects, with an emphasis on the implications for hippocampal processing.

Very selective suppression pulses for clinical MRSI studies of brain and prostate cancer.

Focal three-dimensional magnetic resonance spectroscopic imaging (3D MRSI) methods based on conventional point resolved spectroscopy (PRESS) localization are compromised by the geometric restrictions in volume prescription and by chemical shift registration errors. Outer volume saturation (OVS) pulses have been applied to address the geometric limits, but conventional OVS pulses do little to overcome chemical shift registration error, are not particularly selective, and often leave substantial signals that can degrade the spectra of interest. In this paper, an optimized sequence of quadratic phase pulses is introduced to provide very selective spatial suppression with improved B1 and T1 insensitivity. This method was then validated in volunteer studies and in clinical 3D MRSI exams of brain tumors and prostate cancer.

Mutual Inductance in the Bird-Cage Resonator

Formulas are derived to account for the effect of the mutual inductances, between all meshes, upon the electrical resonance spectra bird-cage resonators, and similar structures such as the TEM resonator of P. K. H. Roschmann (United States Patent 4,746,866) and J. T. Vaughan et al. (Magn. Reson. Med. 32, 206, 1994). The equations are parameterized in terms of isolated mesh frequencies and coupling coefficients, and ought therefore apply not only to simple magnetic couplings used in the derivation, but to electromagnetic couplings as well. A method for measuring the coupling coefficients-applicable to shielded as well as unshielded resonators-is described, based upon the splitting of frequencies in pairs of coupled resonators; and detailed comparisons are given between calculated and measured resonance spectra: for bird-cage resonators, with and without shields, and for the TEM resonator.

Selective, in vivo observation of [5-15N]glutamine amide protons in rat brain by 1H-15N heteronuclear multiple-quantum-coherence transfer NMR.

The amide protons of [5-15N]glutamine were selectively observed in vivo in the brains of anesthetized, spontaneously breathing rats after intravenous 15NH4+ infusion by 1H-15N heteronuclear multiple-quantum-coherence (HMQC) transfer NMR at 200 MHz for 1H. The peak intensity of the upfield amide proton was proportional to brain [5-15N]glutamine concentration. The 15N-decoupled amide-proton signal was observed in vivo in 2 min of acquisition at a brain [5-15N]glutamine concentration of 7.7 +/- 0.4 mumol/g, in < 8 min at 4.35 +/- 0.15 mumol/g, and in 17-34 min at 2.0 +/- 0.1 mumol/g. 1H signals not coupled to 15N were suppressed by phase cycling. The result suggests that 1H-15N HMQC will be useful for kinetic study of glutamine synthesis in rat brain in vivo at physiological concentrations of brain ammonia.

Amplification or obfuscation: is localization improving our clinical understanding of phosphorus metabolism?

Localization techniques are considered an indispensable part of the clinical spectroscopy examination. The results are often a marked improvement in diagnostic information (amplification), but because of the introduction of new artifacts and the more prolonged examination time, some of the undoubted advantage is lost (obfuscation). There is thus an argument for continued development of more rapid methods of clinical spectroscopy and, if necessary, sacrificing some spatial information.

Baseline deconvolution, phase correction, and signal quantification in Fourier localized spectroscopic imaging.

Lineshapes of spectra obtained through chemical-shift imaging are often distorted due to the delay in sampling necessary for application of phase-encoding gradients. We have developed an automated fitting procedure which simultaneously performs signal quantification, phase correction, and baseline deconvolution of such spectra. The fit is based on the maximum likelihood method and can be implemented in either the time or the frequency domain.

A dual-tuned probe and multiband receiver front end for X-nucleus spectroscopy with proton scout imaging in vivo.

A dual-tuned volume coil probe and a novel multituned receiver front end are described, for spectroscopy in vivo of X nuclei with scout imaging of protons. Detailed circuit information is given for the probe, diplexer, receiver protection switch, and preamplifier.

Metabolic response of glioblastoma to adoptive immunotherapy: detection by phosphorus MR spectroscopy.

In a patient with cerebral glioblastoma, metabolic disturbances were detected within the tumor and in the surrounding brain. Within the volume occupied by the tumor, phosphocreatine (PCr)/adenosine triphosphate was reduced and inorganic phosphate/PCr elevated, indicative of tissue necrosis. Loss of total 31P signal was consistent with reduced metabolite content within the area of tumor defined by CT and magnetic resonance (MR). These studies were accomplished with 31P MR spectroscopy at 2 T, using a volume head coil and the technique of two-dimensional phase-encoding to map regional metabolism across the entire cerebral cortex in voxels of 30 cm3. Using the same method, only minor variations in 31P metabolism were noted in six normal controls. Treatment with locally placed Interleukin-2 activated lymphocytes resulted in changes in both MR and 31P MR spectroscopy in the region of the tumor.

Characterization of MR spectroscopic imaging of the human head and limb at 2.0 T.

Using section-select and phase-encoding gradients, the authors obtained phosphorus chemical shift images of the human head and limb. Phosphorus spectra were acquired from planar sections divided into voxels as small as 7 cm3 in calf muscle and 27 cm3 in brain, with total examination times, including setup and proton locator imaging, of roughly 1 hour. Both spin-echo and free induction decay (FID) methods were employed; the FID gave superior results. Signal-to-noise ratios for the beta-adenosine triphosphate and phosphocreatine resonances were as high as 10:1 and 13:1 from volumes of 27 cm3 in brain.

Proton exchange rates in transfer RNA as a function of spermidine and magnesium.

Solvent exchange rates of selected protons were measured by NMR saturation recovery for E. coli tRNAVal, E. colifMet and yeast tRNAPhe, at temperatures from 20 to 40 degrees C, in the presence of 0.12M Na+ and various levels of added spermidine. tRNAVal was also studied with added Mg++. The exchange rates in zero spermidine and Mg++ indicate early melting of the U8 A14 interaction, in accord with thermodynamic melting studies. Exchange rates for secondary protons suggest early melting of the T stem in tRNAfMet and the acceptor stem in tRNAPhe, in contradiction with melting transition assignments from thermodynamic work. Addition of 10 spermidines per tRNA stabilizes the secondary and tertiary interactions more effectively than added Na+, but less so than Mg++. Added spermidine has the curious effect of increasing the exchange rate of the psi 55 N1 proton, while protecting the psi 55 N3 proton from exchange in all three tRNA's. Added Mg++ has the same effect on tRNAVal.