Hue selectivity from recurrent circuitry in Drosophila.

In the perception of color, wavelengths of light reflected off objects are transformed into the derived quantities of brightness, saturation and hue. Neurons responding selectively to hue have been reported in primate cortex, but it is unknown how their narrow tuning in color space is produced by upstream circuit mechanisms. We report the discovery of neurons in the Drosophila optic lobe with hue-selective properties, which enables circuit-level analysis of color processing. From our analysis of an electron microscopy volume of a whole Drosophila brain, we construct a connectomics-constrained circuit model that accounts for this hue selectivity. Our model predicts that recurrent connections in the circuit are critical for generating hue selectivity. Experiments using genetic manipulations to perturb recurrence in adult flies confirm this prediction. Our findings reveal a circuit basis for hue selectivity in color vision.

Hue selectivity from recurrent circuitry in Drosophila.

A universal principle of sensory perception is the progressive transformation of sensory information from broad non-specific signals to stimulus-selective signals that form the basis of perception. To perceive color, our brains must transform the wavelengths of light reflected off objects into the derived quantities of brightness, saturation and hue. Neurons responding selectively to hue have been reported in primate cortex, but it is unknown how their narrow tuning in color space is produced by upstream circuit mechanisms. To enable circuit level analysis of color perception, we here report the discovery of neurons in the Drosophila optic lobe with hue selective properties. Using the connectivity graph of the fly brain, we construct a connectomics-constrained circuit model that accounts for this hue selectivity. Unexpectedly, our model predicts that recurrent connections in the circuit are critical for hue selectivity. Experiments using genetic manipulations to perturb recurrence in adult flies confirms this prediction. Our findings reveal the circuit basis for hue selectivity in color vision.

Exploiting colour space geometry for visual stimulus design across animals.

Colour vision represents a vital aspect of perception that ultimately enables a wide variety of species to thrive in the natural world. However, unified methods for constructing chromatic visual stimuli in a laboratory setting are lacking. Here, we present stimulus design methods and an accompanying programming package to efficiently probe the colour space of any species in which the photoreceptor spectral sensitivities are known. Our hardware-agnostic approach incorporates photoreceptor models within the framework of the principle of univariance. This enables experimenters to identify the most effective way to combine multiple light sources to create desired distributions of light, and thus easily construct relevant stimuli for mapping the colour space of an organism. We include methodology to handle uncertainty of photoreceptor spectral sensitivity as well as to optimally reconstruct hyperspectral images given recent hardware advances. Our methods support broad applications in colour vision science and provide a framework for uniform stimulus designs across experimental systems. This article is part of the theme issue 'Understanding colour vision: molecular, physiological, neuronal and behavioural studies in arthropods'.

Isotopic and Compositional Variations in Single Nuclear Fuel Pellet Particles Analyzed by Nanoscale Secondary Ion Mass Spectrometry.

The Collaborative Materials Exercise (CMX) is organized by the Nuclear Forensics International Technical Working Group, with the aim of advancing the analytical capabilities of the participating organizations and providing feedback on the best approaches to a nuclear forensic investigation. Here, model nuclear fuel materials from the 5th CMX iteration were analyzed using a NanoSIMS 50L (CAMECA) in order to examine inhomogeneities in the 235U/238U ratio and trace element abundance within individual, micrometer scale particles. Two fuel pellets were manufactured for the exercise and labelled CMX-5A and CMX-5B. These pellets were created using different processing techniques, but both had a target enrichment value of 235U/238U = 0.01. Particles from these pellets were isolated for isotopic and trace element analysis. Fifteen CMX-5A particles and 20 CMX-5B particles were analyzed, with both sample types displaying inhomogeneities in the U isotopic composition at a sub-micrometer scale within individual particles. Typical particle diameters were ∼1.5 to 41 µm for CMX-5A and ∼1 to 61 µm for CMX-5B. The CMX-5A particles were shown to be more isotopically homogeneous, with a mean 235U/238U atom ratio of 0.0130 ± 0.0066. The CMX-5B particles showed a predominantly depleted mean 235U/238U atom ratio of 0.0063 ± 0.0094, which is significantly different to the target enrichment value of the pellet and highlights the potential variation of 235U/238U in U fuel pellets at the micrometer scale. This study details the successful application of the NanoSIMS 50L in a mock nuclear forensic investigation by optimizing high-resolution imaging for uranium isotopics.

Circuit Mechanisms Underlying Chromatic Encoding in Drosophila Photoreceptors.

Spectral information is commonly processed in the brain through generation of antagonistic responses to different wavelengths. In many species, these color opponent signals arise as early as photoreceptor terminals. Here, we measure the spectral tuning of photoreceptors in Drosophila. In addition to a previously described pathway comparing wavelengths at each point in space, we find a horizontal-cell-mediated pathway similar to that found in mammals. This pathway enables additional spectral comparisons through lateral inhibition, expanding the range of chromatic encoding in the fly. Together, these two pathways enable efficient decorrelation and dimensionality reduction of photoreceptor signals while retaining maximal chromatic information. A biologically constrained model accounts for our findings and predicts a spatio-chromatic receptive field for fly photoreceptor outputs, with a color opponent center and broadband surround. This dual mechanism combines motifs of both an insect-specific visual circuit and an evolutionarily convergent circuit architecture, endowing flies with the ability to extract chromatic information at distinct spatial resolutions.

Eyes Matched to the Prize: The State of Matched Filters in Insect Visual Circuits.

Confronted with an ever-changing visual landscape, animals must be able to detect relevant stimuli and translate this information into behavioral output. A visual scene contains an abundance of information: to interpret the entirety of it would be uneconomical. To optimally perform this task, neural mechanisms exist to enhance the detection of important features of the sensory environment while simultaneously filtering out irrelevant information. This can be accomplished by using a circuit design that implements specific "matched filters" that are tuned to relevant stimuli. Following this rule, the well-characterized visual systems of insects have evolved to streamline feature extraction on both a structural and functional level. Here, we review examples of specialized visual microcircuits for vital behaviors across insect species, including feature detection, escape, and estimation of self-motion. Additionally, we discuss how these microcircuits are modulated to weigh relevant input with respect to different internal and behavioral states.

Synthesis of functionalised BTPhen derivatives - effects on solubility and americium extraction.

Separation of the minor actinides (Am/Cm) from spent nuclear fuel post-PUREX process is expected to play a key part in new reprocessing methodologies. To date, a number of selective americium extractants from the BTPhen ligand family have been identified. In this investigation, we synthesise 24 novel BTPhens with additional functionality to determine the effects on solubilities and americium extraction capabilities. The data obtained will allow for tuning of steric/electronic properties of BTPhens in order to assist future extractant design.

Rings and threads as linkers in metal-organic frameworks and poly-rotaxanes.

Coordination polymers and metal-organic rotaxane frameworks are reported where the organic linker is replaced by functionalised inorganic clusters that act as bridging ligands.

Probing the structure, conformation, and stereochemical exchange in a family of lanthanide complexes derived from tetrapyridyl-appended cyclen.

A series of lanthanide complexes have been synthesized from 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazacyclododecane. Crystallographic studies indicate that, in the solid phase, all of the lanthanide ions are 9-coordinate and are bound to eight N atoms from the donor ligand, with the ninth site being filled by a counterion or solvent molecule. In solution, time-resolved luminescence studies indicate that the luminescence exhibits contributions from two species corresponding to the nonhydrated and hydrated forms. The NMR spectra in protic media show the presence of two dominant isomers on the NMR time scale; furthermore, the spectra are very different from those obtained for 1,4,7,10-tetraazacyclododecane-N',N'',N''',N''''-tetraacetic acid (DOTA) and its derivatives. The different forms of the complex undergo slow conformational and enantiomeric exchange in solution, which has been measured by NMR. The exchange path has been mapped out by density functional theory calculations and shows multiple metastable conformations (with respect to the dihedral angles of the cyclen ring). This contrasts with the established NMR behavior of DOTA complexes, which has been described by a two-state solution equilibrium.

Luminescent dinuclear lanthanide complexes of 5-Me-HXTA.

The synthesis and characterization of a series of anionic homobimetallic lanthanide complexes of the septadentate chelate 5-Me-HXTA (N,N-(2 hydroxy-5-methyl-1,3-xylylene)bis(N-(carboxymethyl)glycine) is described (Ln = Nd, Sm, Eu, Tb, Dy, Ho, Er, Yb). Single X-ray crystallography confirms that the complexes exist as discrete dimeric pairs in the solid state. Proton NMR, diffusion-ordered spectroscopy, and luminescence solution studies suggest that the binuclear stoichiometry is retained in aqueous solution over a range of analytically useful concentrations. The phenolic chromophores effectively sensitize the visible and near-infrared lanthanide-centered emission in the terbium, neodymium, and ytterbium derivatives, giving rise to particularly long-lived green and near-infrared emission. The terbium complex displays a high quantum yield of around 50% in aqueous solution with a low detection limit of 1 x 10(-12) M, rendering this compound a potential candidate for time-resolved applications.

Self-assembled, kinetically locked, Ru(II)-based metallomacrocycles: physical, structural, and modeling studies.

By using a "complex as ligand approach," the metal-ion-templated self-assembly of heterometallic tetranuclear metallomacrocycles containing kinetically locked Ru(II) centers is described. Depending on the metal-ion template employed in the self-assembly process, the final macrocycle can be kinetically labile or inert. Electrochemical studies reveal that the kinetically inert macrocycles display reversible Ru(III/II) oxidation couples. The crystal structure of a kinetically inert Ru2Re2 macrocycles reveals a structurally complex palmate anion-binding pocket. Host-guest studies carried out with the same macrocyle in organic solvents reveals that the complex functions as a luminescent sensor for anions and that binding affinity and luminescent modulation is dependent on the structural nature and charge of the guest anion. Computational density functional theory (DFT) studies support the hypothesis that the luminescence of the macrocycle is from a 3MLCT state and further suggests that the observed guest-induced luminescence changes are most likely due to modulation of nonradiative decay processes.

Reactions of benzene oxide with thiols including glutathione.

S-Phenylmercapturic acid is a minor metabolite of benzene used as a biomarker for human benzene exposures. The reaction of intracellular glutathione with benzene oxide-oxepin, the initial metabolite of benzene, is presumed to give 1-(S-glutathionyl)-cyclohexa-3,5-dien-2-ol, which undergoes dehydration to S-phenylglutathione, the precursor of S-phenylmercapturic acid. To validate the proposed route to S-phenylglutathione, reactions of benzene oxide-oxepin with glutathione and other sulfur nucleophiles have been studied. The reaction of benzene oxide with an excess of aqueous sodium sulfide, followed by acetylation, gave bis-(6-trans-5-acetoxycyclohexa-1,3-dienyl)sulfide, the structure of which was proved by X-ray crystallography. Reactions of benzene oxide-oxepin in a 95:5 (v/v) mixture of phosphate buffer in D2O with (CD3)2SO were monitored by 1H NMR spectroscopy. In the absence of glutathione, the half-life of benzene oxide-oxepin was ca. 34 min at 25 degrees C and pD 7.0. The half-life was not affected in the range of 2-15 mM glutathione in the presence and absence of a commercial sample of human glutathione S-transferase (at pH 7.0, 8.0, 8.5, or 10.0). The adduct 1-(S-glutathionyl)-cyclohexa-3,5-diene-2-ol was identified in these reaction mixtures, especially at higher pH, by mass spectrometry and by its acid-catalyzed decomposition to S-phenylglutathione. Incubation of benzene oxide with N-acetyl-L-cysteine at 37 degrees C and pH 10.0 and subsequent mass spectrometric analysis of the mixture showed formation of pre-S-phenylmercapturic acid and the dehydration product, S-phenylmercapturic acid. The data validate the premise that benzene oxide-oxepin can be captured by glutathione to give (1R,2R)- and/or (1S,2S)-1-(S-glutathionyl)-cyclohexa-3,5-dien-2-ol, which dehydrate to S-phenylglutathione. The capture is a relatively inefficient process at pH 7 that is accelerated at higher pH. These studies account for the observation that the metabolism of benzene is dominated by the formation of phenol. The pathway leading to S-phenylmercapturic acid is necessarily minor on account of the low efficiency of benzene oxide capture by glutathione at pH 7 vs spontaneous rearrangement to phenol.

Synthesis and luminescence properties of lanthanide complexes incorporating a hydralazine-derived chromophore.

Reaction of 1-hydrazinophthalazine with chloroacetyl chloride yields 3-chloromethyl-1,2,4-triazolo-phthalazine. Reaction of this product with the tris tert-butyl ester of DO3A yields a triazolophthalazine appended macrocycle. Hydrolysis and complexation with lanthanide ions gives access to a series of lanthanide complexes (Ln = Nd, Eu, Yb, Er); these are all luminescent and exhibit sensitisation of the lanthanide centre by the chromophore.

Synthesis, structure and magnetism of a novel carboxylate bridged manganese(II) sheet structure containing the first unsupported aqua bridge.

The structural characterisation of a 2D sheet complex [[Mn2(Hetheidi)2(mu-H2O)(H2O)].3H2O]n 1 [Hetheidi =DL-N-(1-hydroxymethylpropyl)iminodiacetic acid] assembled from the tetradentate ligand Hetheidi and MnCl2 reveals the presence of rare unsupported mu-aqua bridges and novel hydrogen-bonded water channels, which bind the sheets together.

Self-assembled polynuclear clusters derived from some flexible polydentate dihydrazide ligands.

Polynuclear manganese(II), cobalt(II)/(III), iron(II)/(III) and nickel(II) complexes of a group of flexible polydentate dihydrazone ligands, based on pyridine-2,6-dipicolinic (A), oxalic (B) and malonic (C) subunits are described. Structural details are reported for the linear dinuclear complexes [Ni2(2poap)2(H2O)2](NO3)4 . 2CH3OH . 2.5H2O (1), [Mn2(pttp)(NO3)2(CH3OH)2(H2O)2](NO3)2 . H2O (2) and [Mn2(mapttp)2(NO3)2(H2O)2](NO3)2 . 10H2O (3), a square tetranuclear complex [Co4(pttp)4]Br6 . 9H2O (4), a tetranuclear tetrahedral complex [Ni4(pttp)6](BF4)6F2 . 14H2O (7), and a mixed spin state tetranuclear Ni(II) complex [(2pyoap)2Ni4(CH3OH)4] . 1.5CH3OH (10), with a diamond-like arrangement of metal ions. The paramagnetic metal centers are well separated in each case, leading to weak antiferromagnetic coupling or non-existent spin exchange.

A centred, elongated "ferric tetrahedron" with an S= 15/2 spin ground state.

The reaction of anhydrous FeCl(3) with 1H-benzotriazole-1-methanol (Bta-CH(2)OH) in MeOH produces the pentanuclear complex [Fe(5)O(2)(OMe)(2)(Bta)(4)(BtaH)(MeOH)(5)Cl(5)], containing a distorted tetrahedron of four Fe ions centred on a fifth. The central Fe is antiferromagnetically coupled to the peripheral Fe ions resulting in an S= 15/2 spin ground state.