Synthesis of organic salts with large second-order optical nonlinearities

A series of organic salts, in which the cation has been designed to have a large molecular hyperpolarizability, has been prepared. Variation of the counterion (anion) in many cases leads to materials with large powder second harmonic generation efficiencies, the highest of which is roughly 1000 times that of a urea reference.     

A unified description of linear and nonlinear polarization in organic polymethine dyes

An internal or external electric field F can drive the chemical structure, bond order alternation, and electronic structure of linear polymethine dyes from a neutral, bond-alternated, polyene-like structure, through a cyanine-like structure, and ultimately to a zwitterionic (charge-separated) bond-alternated structure. As the structure evolves under the influence of F, the linear polarizability alpha, the first hyperpolarizability beta, and the second hyperpolarizability gamma are seen to be derivatives, with respect to F, of their next lower order polarization (for alpha) or polarizability (for beta and gamma). These derivative relations provide a unified picture of the dependence of the polarizability and hyperpolarizabilities on the structure in linear polymethine dyes. In addition, they allow for predictions of structure-property relations of higher order hyperpolarizabilities.     

Predicting Cotton Lint Yield Maps from Aerial Photographs

It is generally accepted that aerial images of growing crops provide spatial and temporal information about crop growth conditions and may even be indicative of crop yield. The focus of this study was to develop a straightforward technique for creating predictive cotton yield maps from aerial images. A total of ten fields in southern Georgia, USA, were studied during three growing seasons. Conventional (true color) aerial photographs of the fields were acquired during the growing season in two to four week intervals. The aerial photos were then digitized and analyzed using an unsupervised classification function of image analysis software. During harvest, conventional yield maps were created for each of the fields using a cotton picker mounted yield monitor. Classified images and yield maps were compared quantitatively and qualitatively. A pixel by pixel comparison of the classified images and yield maps showed that spatial agreement between the two gradually increased in the weeks after planting, maintained spatial agreement of between 40% and 60% during weeks eight to fourteen, and then gradually declined again. The highest spatial agreement between a classified image and a yield map was 78%. The highest average agreement was 52% and occurred 9.9 weeks after planting. The visual similarity between the classified images and the yield maps were striking. In all cases, the dates with the best visual agreement occurred between eight and ten weeks after planting, and generally, during July for southern Georgia. This method offers great potential for offering cotton farmers early-season maps that predict the spatial distribution of yield. Although these maps can not provide magnitudes, they clearly show the resulting yield patterns. With inherent knowledge of past performance, farmers can use this information to allocate resources, address crop growth problems, and, perhaps, improve the profitability of their farm operation. These maps are well suited to be offered to farmers as a service by a crop consultant or a cooperative.     

Magnetic field-tuned quantum criticality in the metallic ruthenate Sr3Ru2O7

The concept of quantum criticality is proving to be central to attempts to understand the physics of strongly correlated electrons. Here, we argue that observations on the itinerant metamagnet Sr3Ru2O7 represent good evidence for a new class of quantum critical point, arising when the critical end point terminating a line of first-order transitions is depressed toward zero temperature. This is of interest both in its own right and because of the convenience of having a quantum critical point for which the tuning parameter is the magnetic field. The relationship between the resultant critical fluctuations and novel behavior very near the critical field is discussed.     

N-Methylmetanephrine: Excretion by Juvenile Psychotics

Three out of 18 psychotic children excreted N-methylmetanephrine, a metabolite of N-methylepinephrine. It is not clear whether this tertiary amine plays a part in causing some forms of psychosis or is merely a secondary result of mental dysfunction. Urinary excretion of bufotenin and of 3,4-dimethoxyphenylethylamine, each of which has been reported elevated in some adult schizophrenics, was not unusual in these children.     

Prevention of organ allograft rejection by a specific Janus kinase 3 inhibitor

Because of its requirement for signaling by multiple cytokines, Janus kinase 3 (JAK3) is an excellent target for clinical immunosuppression. We report the development of a specific, orally active inhibitor of JAK3, CP-690,550, that significantly prolonged survival in a murine model of heart transplantation and in cynomolgus monkeys receiving kidney transplants. CP-690,550 treatment was not associated with hypertension, hyperlipidemia, or lymphoproliferative disease. On the basis of these preclinical results, we believe JAK3 blockade by CP-690,550 has potential for therapeutically desirable immunosuppression in human organ transplantation and in other clinical settings.     

Amplification of acetylcholine-binding catenanes from dynamic combinatorial libraries

Directed chemical synthesis can produce a vast range of molecular structures, but the intended product must be known at the outset. In contrast, evolution in nature can lead to efficient receptors and catalysts whose structures defy prediction. To access such unpredictable structures, we prepared dynamic combinatorial libraries in which reversibly binding building blocks assemble around a receptor target. We selected for an acetylcholine receptor by adding the neurotransmitter to solutions of dipeptide hydrazones [proline-phenylalanine or proline-(cyclohexyl)alanine], which reversibly combine through hydrazone linkages. At thermodynamic equilibrium, the dominant receptor structure was an elaborate [2]-catenane consisting of two interlocked macrocyclic trimers. This complex receptor with a 100 nM affinity for acetylcholine could be isolated on a preparative scale in 67% yield.     

Targeting of diacylglycerol degradation to M1 muscarinic receptors by beta-arrestins

Seven-transmembrane receptor (7TMR) signaling is transduced by second messengers such as diacylglycerol (DAG) generated in response to the heterotrimeric guanine nucleotide-binding protein Gq and is terminated by receptor desensitization and degradation of the second messengers. We show that beta-arrestins coordinate both processes for the Gq-coupled M1 muscarinic receptor. beta-Arrestins physically interact with diacylglycerol kinases (DGKs), enzymes that degrade DAG. Moreover, beta-arrestins are essential for conversion of DAG to phosphatidic acid after agonist stimulation, and this activity requires recruitment of the beta-arrestin-DGK complex to activated 7TMRs. The dual function of beta-arrestins, limiting production of diacylglycerol (by receptor desensitization) while enhancing its rate of degradation, is analogous to their ability to recruit adenosine 3',5'-monophosphate phosphodiesterases to Gs-coupled beta2-adrenergic receptors. Thus, beta-arrestins can serve similar regulatory functions for disparate classes of 7TMRs through structurally dissimilar enzymes that degrade chemically distinct second messengers.     

Formation of a nematic fluid at high fields in Sr3Ru2O7

In principle, a complex assembly of strongly interacting electrons can self-organize into a wide variety of collective states, but relatively few such states have been identified in practice. We report that, in the close vicinity of a metamagnetic quantum critical point, high-purity strontium ruthenate Sr3Ru2O7 possesses a large magnetoresistive anisotropy, consistent with the existence of an electronic nematic fluid. We discuss a striking phenomenological similarity between our observations and those made in high-purity two-dimensional electron fluids in gallium arsenide devices.     

Targeting of cyclic AMP degradation to beta 2-adrenergic receptors by beta-arrestins

Catecholamines signal through the beta2-adrenergic receptor by promoting production of the second messenger adenosine 3',5'-monophosphate (cAMP). The magnitude of this signal is restricted by desensitization of the receptors through their binding to beta-arrestins and by cAMP degradation by phosphodiesterase (PDE) enzymes. We show that beta-arrestins coordinate both processes by recruiting PDEs to activated beta2-adrenergic receptors in the plasma membrane of mammalian cells. In doing so, the beta-arrestins limit activation of membrane-associated cAMP-activated protein kinase by simultaneously slowing the rate of cAMP production through receptor desensitization and increasing the rate of its degradation at the membrane.