Self-assembly of a [2]pseudorota[3]catenane in water.

A donor-acceptor [3]catenane incorporating two cyclobis(paraquat-p-phenylene) rings linked together by a dinaphtho[50]crown-14 macrocycle possesses a π-electron-deficient pocket. Contrary to expectation, negligible binding of a hexaethylene glycol chain interrupted in its midriff by a π-electron-rich 1,5-dioxynaphthalene unit was observed in acetonitrile. However, a fortuitous solid-state superstructure of the expected 1:1 complex revealed its inability to embrace any stabilizing [C-H···O] interactions between the clearly unwelcome guest and the host reluctantly accommodating it.

A within-subject ERP and fMRI investigation of orientation-specific recognition memory for pictures.

Despite a large body of recognition memory research, its temporal, measured with ERPs, and spatial, measured with fMRI, substrates have never been investigated in the same subjects. In the present study, we obtained this information in parallel sessions, in which subjects studied and recognized images of visual objects and their orientation. The results showed that ERP-familiarity processes between 240 and 440 ms temporally preceded recollection processes and were structurally associated with prefrontal brain regions.

Extending local canonical correlation analysis to handle general linear contrasts for FMRI data.

Local canonical correlation analysis (CCA) is a multivariate method that has been proposed to more accurately determine activation patterns in fMRI data. In its conventional formulation, CCA has several drawbacks that limit its usefulness in fMRI. A major drawback is that, unlike the general linear model (GLM), a test of general linear contrasts of the temporal regressors has not been incorporated into the CCA formalism.

A preliminary study of functional abnormalities in aMCI subjects during different episodic memory tasks.

Functional magnetic resonance imaging (fMRI) is an important imaging modality to understand the neurodegenerative course of mild cognitive impairment (MCI) and early Alzheimer's disease (AD), because the memory dysfunction may occur before structural degeneration is obvious. In this research, we investigated the functional abnormalities of subjects with amnestic MCI (aMCI) using three episodic memory paradigms that are relevant to different memory domains in both encoding and recognition phases. Both whole-brain analysis and region-of-interest (ROI) analysis of the medial temporal lobes (MTL), which are central to the memory formation and retrieval, were used to compare the efficiency of the different memory paradigms and the functional difference between aMCI subjects and normal control subjects.

Polyporous metal-coordination frameworks.

Starting from a chiral building block--α-cyclodextrin--and rubidium salts, the crystallization of a complex of chiral helices, which constitute a "green" porous coordination polymer, has been realized. Cyclodextrin molecules coordinated by rubidium ions form porous, infinitely long left-handed helical channels, interdigitated with each other. A theoretical examination of the potential of this new material to act as a medium for chiral separation is presented.

Optimization of contrast detection power with probabilistic behavioral information.

Recent progress in the experimental design for event-related fMRI experiments made it possible to find the optimal stimulus sequence for maximum contrast detection power using a genetic algorithm. In this study, a novel algorithm is proposed for optimization of contrast detection power by including probabilistic behavioral information, based on pilot data, in the genetic algorithm. As a particular application, a recognition memory task is studied and the design matrix optimized for contrasts involving the familiarity of individual items (pictures of objects) and the recollection of qualitative information associated with the items (left/right orientation).

Metal-organic frameworks incorporating copper-complexed rotaxanes.

[Image: see text] A copper coordinated [2]pseudorotaxanate which reacts with zinc nitrate to form an extended structure, consisting of three-fold interpenetrated networks, retains most of its solution-state chemistry including its ability to undergo electronic switching of some of the copper(I) ions under redox control.

Onset of three-centre, four-electron bonding in peri-substituted acenaphthenes: a structural and computational investigation.

Two series of sterically crowded peri-substituted acenaphthenes have been prepared, containing mixed halogen-chalcogen functionalities at the 5,6-positions in A1-A6 (Acenap[X][EPh] (Acenap = acenaphthene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in A7-A12 (Acenap[EPh][E'Ph] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te). The related dihalide compounds A13-A16 Acenap[XX'] (XX' = BrBr, II, IBr, ClCl) have also been prepared. Distortion of the acenaphthene framework away from the ideal was studied as a function of the steric bulk of the interacting halogen and chalcogen atoms occupying the peri-positions.

2,5-Diaryl-1,3,4-selenadiazoles prepared from Woollins' reagent.

Two polymorphs of 2,5-diphenyl-1,3,4-selenadiazole, C(14)H(10)N(2)Se, denoted (Ia) and (Ib), and a new polymorph of 2,5-bis(thiophen-2-yl)-1,3,4-selenadiazole, C(10)H(6)N(2)S(2)Se, (IIb), form on crystallization of the compounds, prepared using Woollins' reagent (2,4-diphenyl-1,3-diselenadiphosphetane 2,4-diselenide). These compounds, along with 2-(4-chlorophenyl)-5-phenyl-1,3,4-selenadiazole, C(14)H(9)ClN(2)Se, (III), and 2-(furan-2-yl)-5-(p-tolyl)-1,3,4-selenadiazole, C(13)H(10)N(2)OSe, (IV), show similar intermolecular interactions, with π-π stacking, C-H..

Nanoporous carbohydrate metal-organic frameworks.

The binding of alkali and alkaline earth metal cations by macrocyclic and diazamacrobicyclic polyethers, composed of ordered arrays of hard oxygen (and nitrogen) donor atoms, underpinned the development of host-guest supramolecular chemistry in the 1970s and 1980s. The arrangement of -OCCO- and -OCCN- chelating units in these preorganized receptors, including, but not limited to, crown ethers and cryptands, is responsible for the very high binding constants observed for their complexes with Group IA and IIA cations. The cyclodextrins (CDs), cyclic oligosaccharides derived microbiologically from starch, also display this -OCCO- bidentate motif on both their primary and secondary faces.

Aberrant default mode network in subjects with amnestic mild cognitive impairment using resting-state functional MRI.

Amnestic mild cognitive impairment (aMCI) is a syndrome associated with faster memory decline than normal aging and frequently represents the prodromal phase of Alzheimer's disease. When a person is not actively engaged in a goal-directed task, spontaneous functional magnetic resonance imaging (fMRI) signals can reveal functionally connected brain networks, including the so-called default mode network (DMN). To date, only a few studies have investigated DMN functions in aMCI populations.

2,4,5-Triphenyl-1,3,2-dioxa-phospho-lan-2-one.

The dioxaphospho-lane ring in the title compound, C(20)H(17)O(3)P, adopts an envelope conformation about one of the ring carbons. The benzene rings of the compound do not form face-to-face π-π inter-actions, instead weak C-H⋯π inter-actions occur between adjacent mol-ecules. The methine H atoms on the dioxaphospho-lane ring form weak C-H⋯O hydrogen bonds to the oxide group of an adjacent mol-ecule.

2-Phenyl-5-(p-tol-yl)-1,3,4-oxadiazole.

The title compound, C(15)H(12)N(2)O, adopts the expected near-planar geometry, the phenyl and tolyl rings being inclined relative to the oxadiazole ring by 3.8 (3) and 8.3 (2)°, respectively.

Phen-yl(2,4,5-triphenyl-cyclo-penta-1,4-dien-1-yl)methanone.

The title compound, C(30)H(22)O, does not form face-to-face π-π inter-actions despite the presence of four phenyl rings within the compound. Instead weak C-H⋯π inter-actions occur between adjacent mol-ecules, with C⋯C contact distances in the range 3.633 (4)-3.

2-(4-Fluoro-phen-yl)-3-methyl-1H-indole.

The indole N-H hydrogen in the title compound, C(15)H(12)FN, does not display classical hydrogen bonding. Rather it forms an interaction with the π system of an adjacent indole, resulting in weakly inter-acting chains along the [001] direction.

Bis(furan-2-ylcarbon-yl) diselenide.

The title mol-ecule, C(10)H(6)O(4)Se(2), lies on a twofold rotation axis. The Se-Se bond length of 2.305 (3) Å is similar to that in diphenyl diselenide [2.

Altered default network activity in obesity.

The regulation of energy intake is a complex process involving the integration of homeostatic signals and both internal and external sensory inputs. To better understand the neurobiology of this process and how it may be dysfunctional in obesity, this study examined activity of the brain's "default network" in reduced-obese (RO) as compared to lean individuals. The default network is a group of functionally connected brain regions thought to play an important role in internally directed cognitive activity and the interplay between external and internal sensory processing.

Nicotine effects on default mode network during resting state.

Rationale: The default mode network (DMN), one of several resting-state networks (RSN) in the brain, is thought to be involved in self-referential thought, awareness, and episodic memories. Nicotine improves cognitive performance, in part by improving attention. Nicotinic agonists have been shown to decrease activity in regions within DMN and increase activity in regions involved in visual attention during effortful processing of external stimuli.

The gas-phase structure and some reactions of the bulky primary silane (Me(3)Si)(3)CSiH(3) and the solid-state structure of the bulky dialkyl disilane [(Me(3)Si)(3)CSiH(2)](2).

The molecular structure of the bulky primary silane, (Me(3)Si)(3)CSiH(3), in the gas phase has been determined by electron diffraction. Photolysis of (Me(3)Si)(3)CSiH(3) affords a convenient route to the bulky dialkyl disilane, [(Me(3)Si)(3)CSiH(2)](2), which is the first 1,2-dialkyldisilane to be structurally characterised by single-crystal X-ray diffraction. The disilane has an unusually large Si-Si-C angle of 120.

A general design platform for ionic liquid ions based on bridged multi-heterocycles with flexible symmetry and charge.

A conceptual design platform for new ionic liquids with variable heterocycles, bridges, symmetry, and charge was developed using simple alkylation, click, and ionic liquid chemistries and demonstrated with 1-(2-(5-tetrazolidyl)ethyl)-3-(5-1H-tetrazolyl)methylimidazolium and its conversion into room-temperature ionic liquids as cation or as anion.

The gas-phase structure of octaphenyloctasilsesquioxane Si8O12Ph8 and the crystal structures of Si8O12(p-tolyl)8 and Si8O12(p-ClCH2C6H4)8.

The equilibrium molecular structure of octaphenyloctasilsesquioxane Si(8)O(12)Ph(8) in the gas phase has been determined by electron diffraction. It was found to have D(4) point-group symmetry, with Si-O bond lengths of 1.634(15)-1.

Ionic liquid-based routes to conversion or reuse of recycled ammonium perchlorate.

New, potentially green, and efficient synthetic routes for the remediation and/or re-use of perchlorate-based energetic materials have been developed. Four simple organic imidazolium- and phosphonium-based perchlorate salts/ionic liquids have been synthesized by simple, inexpensive, and nonhazardous methods, using ammonium perchlorate as the perchlorate source. By appropriate choice of the cation, perchlorate can be incorporated into an ionic liquid which serves as its own electrolyte for the electrochemical reduction of the perchlorate anion, allowing for the regeneration of the chloride-based parent ionic liquid.

Quantitative approaches to functional MRI: applications in epilepsy.

The application of functional magnetic resonance imaging (fMRI) to elucidation of seizures and epilepsy has been built primarily upon a framework derived from cortical responses to periodic sensory (and cognitive) stimuli. This analytical approach relies upon assumptions that may be less applicable to the problem of seizure origination. Because of the heterogeneous and complex nature of seizures, a number of quantitative methodologies have been derived to understand fMRI changes that are associated with epileptiform neural activity.

Independent component analysis in the presence of noise in fMRI.

A noisy version of independent component analysis (noisy ICA) is applied to simulated and real functional magnetic resonance imaging (fMRI) data. The noise covariance is explicitly modeled by an autoregressive (AR) model of order 1. The unmixing matrix of the data is determined using a variant of the FastICA algorithm based on Gaussian moments.