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1.
J Neurosci ; 43(29): 5378-5390, 2023 07 19.
Artigo em Inglês | MEDLINE | ID: mdl-37369590

RESUMO

Radial frequency (RF) patterns, created by sinusoidal modulations of a circle's radius, are processed globally when RF is low. These closed shapes therefore offer a useful way to interrogate the human visual system for global processing of curvature. RF patterns elicit greater responses than those to radial gratings in V4 and more anterior face-selective regions of the ventral visual pathway. This is largely consistent with work on nonhuman primates showing curvature processing emerges in V4, but is evident also higher up the ventral visual stream. Rather than contrasting RF patterns with other stimuli, we presented them at varied frequencies in a regimen that allowed tunings to RF to be derived from 8 human participants (3 female). We found tuning to low RF in lateral occipital areas and to some extent in V4. In a control experiment, we added a high-frequency ripple to the stimuli disrupting the local contour. Low-frequency tuning to these stimuli remained in the ventral visual stream, underscoring its role in global processing of shape curvature. We then used representational similarity analysis to show that, in lateral occipital areas, the neural representation was related to stimulus similarity, when it was computed with a model that captured how stimuli are perceived. We therefore show that global processing of shape curvature emerges in the ventral visual stream as early as V4, but is found more strongly in lateral occipital regions, which exhibit responses and representations that relate well to perception.SIGNIFICANCE STATEMENT We show that tuning to low radial frequencies, known to engage global shape processing mechanisms, was localized to lateral occipital regions. When low-level stimulus properties were accounted for such tuning emerged in V4 and LO2 in addition to the object-selective region LO. We also documented representations of global shape properties in lateral occipital regions, and these representations were predicted well by a proxy of the perceptual difference between the stimuli.


Assuntos
Percepção de Forma , Vias Visuais , Animais , Humanos , Feminino , Vias Visuais/fisiologia , Rádio (Anatomia) , Reconhecimento Visual de Modelos/fisiologia , Lobo Occipital , Percepção de Forma/fisiologia , Estimulação Luminosa
2.
Chemistry ; : e202402364, 2024 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-38985739

RESUMO

Controlling and understanding charge state and metal coordination in carbon nanomaterials is crucial to harnessing their unique properties. Here we describe the synthesis of the well-defined fulleride complex [{(Mesnacnac)Mg}6C70], 2, (Mesnacnac)=HC(MeCNMes)2, Mes=2,4,6-Me3C6H2, from the reaction of the ß-diketiminate magnesium(I) complex [{(Mesnacnac)Mg}2] with C70 in aromatic solvents. The molecular structure of complex 2 was determined, providing the first high-quality structural study of a complex with the C70 6- ion. In combination with solution state NMR spectroscopic and DFT computational studies, the changes in geometry and charge distribution in the various atom and bond types of the fulleride unit were investigated. Additionally, the influence of the (Mesnacnac)Mg+ cations on the global and local fulleride coordination environment was examined.

3.
Molecules ; 26(23)2021 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-34885796

RESUMO

The reaction of [{(Arnacnac)Mg}2] (Arnacnac = HC{MeC(NAr)}2, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures afforded the hexameric magnesium 4-pyridyl complex [{(Arnacnac)Mg(4-C5H4N)}6] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprising tetrahedral (Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared with other ring systems. [(Dipnacnac)Mg(DMAP)(NMe2)] was structurally characterised as a by-product.

4.
J Neurophysiol ; 123(1): 224-233, 2020 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-31774368

RESUMO

The visual system adapts to its recent history. A phenomenon related to this is repetition suppression (RS), a reduction in neural responses to repeated compared with nonrepeated visual input. An intriguing hypothesis is that the timescale over which RS occurs across the visual hierarchy is tuned to the temporal statistics of visual input features, which change rapidly in low-level areas but are more stable in higher level areas. Here, we tested this hypothesis by studying the influence of the temporal lag between successive visual stimuli on RS throughout the visual system using functional (f)MRI. Twelve human volunteers engaged in four fMRI sessions in which we characterized the blood oxygen level-dependent response to pairs of repeated and nonrepeated natural images with interstimulus intervals (ISI) ranging from 50 to 1,000 ms to quantify the temporal tuning of RS along the posterior-anterior axis of the visual system. As expected, RS was maximal for short ISIs and decayed with increasing ISI. Crucially, however, and against our hypothesis, RS decayed at a similar rate in early and late visual areas. This finding challenges the prevailing view that the timescale of RS increases along the posterior-anterior axis of the visual system and suggests that RS is not tuned to temporal input regularities.NEW & NOTEWORTHY Visual areas show reduced neural responses to repeated compared with nonrepeated visual input, a phenomenon termed repetition suppression (RS). Here we show that RS decays at a similar rate in low- and high-level visual areas, suggesting that the short-term decay of RS across the visual hierarchy is not tuned to temporal input regularities. This may limit the specificity with which the mechanisms underlying RS could optimize the processing of input features across the visual hierarchy.


Assuntos
Adaptação Fisiológica/fisiologia , Neuroimagem Funcional , Reconhecimento Visual de Modelos/fisiologia , Córtex Visual/fisiologia , Adulto , Feminino , Humanos , Imageamento por Ressonância Magnética , Masculino , Adulto Jovem
5.
Neuroimage ; 197: 785-791, 2019 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-28687519

RESUMO

The cortex is a massively recurrent network, characterized by feedforward and feedback connections between brain areas as well as lateral connections within an area. Feedforward, horizontal and feedback responses largely activate separate layers of a cortical unit, meaning they can be dissociated by lamina-resolved neurophysiological techniques. Such techniques are invasive and are therefore rarely used in humans. However, recent developments in high spatial resolution fMRI allow for non-invasive, in vivo measurements of brain responses specific to separate cortical layers. This provides an important opportunity to dissociate between feedforward and feedback brain responses, and investigate communication between brain areas at a more fine- grained level than previously possible in the human species. In this review, we highlight recent studies that successfully used laminar fMRI to isolate layer-specific feedback responses in human sensory cortex. In addition, we review several areas of cognitive neuroscience that stand to benefit from this new technological development, highlighting contemporary hypotheses that yield testable predictions for laminar fMRI. We hope to encourage researchers with the opportunity to embrace this development in fMRI research, as we expect that many future advancements in our current understanding of human brain function will be gained from measuring lamina-specific brain responses.


Assuntos
Mapeamento Encefálico/métodos , Encéfalo/fisiologia , Neurociência Cognitiva/métodos , Imageamento por Ressonância Magnética/métodos , Animais , Neurociência Cognitiva/tendências , Humanos
6.
Hum Brain Mapp ; 39(10): 3813-3826, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-29968956

RESUMO

Symmetry is effortlessly perceived by humans across changes in viewing geometry. Here, we re-examined the network subserving symmetry processing in the context of up-to-date retinotopic definitions of visual areas. Responses in object selective cortex, as defined by functional localizers, were also examined. We further examined responses to both frontoparallel and slanted symmetry while manipulating attention both toward and away from symmetry. Symmetry-specific responses first emerge in V3 and continue across all downstream areas examined. Of the retinotopic areas, ventral occipital VO1 showed the strongest symmetry response, which was similar in magnitude to the responses observed in object selective cortex. Neural responses were found to increase with both the coherence and folds of symmetry. Compared to passive viewing, drawing attention to symmetry generally increased neural responses and the correspondence of these neural responses with psychophysical performance. Examining symmetry on the slanted plane found responses to again emerge in V3, continue through downstream visual cortex, and be strongest in VO1 and LOB. Both slanted and frontoparallel symmetry evoked similar activity when participants performed a symmetry-related task. However, when a symmetry-unrelated task was performed, fMRI responses to slanted symmetry were reduced relative to their frontoparallel counterparts. These task-related changes provide a neural signature that suggests slant has to be computed ahead of symmetry being appropriately extracted, known as the "normalization" account of symmetry processing. Specifically, our results suggest that normalization occurs naturally when attention is directed toward symmetry and orientation, but becomes interrupted when attention is directed away from these features.


Assuntos
Mapeamento Encefálico/métodos , Reconhecimento Visual de Modelos/fisiologia , Percepção Espacial/fisiologia , Córtex Visual/fisiologia , Adulto , Feminino , Humanos , Imageamento por Ressonância Magnética , Masculino , Córtex Visual/diagnóstico por imagem , Adulto Jovem
7.
J Neurosci ; 36(21): 5763-74, 2016 05 25.
Artigo em Inglês | MEDLINE | ID: mdl-27225766

RESUMO

UNLABELLED: Representations in early visual areas are organized on the basis of retinotopy, but this organizational principle appears to lose prominence in the extrastriate cortex. Nevertheless, an extrastriate region, such as the shape-selective lateral occipital cortex (LO), must still base its activation on the responses from earlier retinotopic visual areas, implying that a transition from retinotopic to "functional" organizations should exist. We hypothesized that such a transition may lie in LO-1 or LO-2, two visual areas lying between retinotopically defined V3d and functionally defined LO. Using a rapid event-related fMRI paradigm, we measured neural similarity in 12 human participants between pairs of stimuli differing along dimensions of shape exemplar and shape complexity within both retinotopically and functionally defined visual areas. These neural similarity measures were then compared with low-level and more abstract (curvature-based) measures of stimulus similarity. We found that low-level, but not abstract, stimulus measures predicted V1-V3 responses, whereas the converse was true for LO, a double dissociation. Critically, abstract stimulus measures were most predictive of responses within LO-2, akin to LO, whereas both low-level and abstract measures were predictive for responses within LO-1, perhaps indicating a transitional point between those two organizational principles. Similar transitions to abstract representations were not observed in the more ventral stream passing through V4 and VO-1/2. The transition we observed in LO-1 and LO-2 demonstrates that a more "abstracted" representation, typically considered the preserve of "category-selective" extrastriate cortex, can nevertheless emerge in retinotopic regions. SIGNIFICANCE STATEMENT: Visual areas are typically identified either through retinotopy (e.g., V1-V3) or from functional selectivity [e.g., shape-selective lateral occipital complex (LOC)]. We combined these approaches to explore the nature of shape representations through the visual hierarchy. Two different representations emerged: the first reflected low-level shape properties (dependent on the spatial layout of the shape outline), whereas the second captured more abstract curvature-related shape features. Critically, early visual cortex represented low-level information but this diminished in the extrastriate cortex (LO-1/LO-2/LOC), in which the abstract representation emerged. Therefore, this work further elucidates the nature of shape representations in the LOC, provides insight into how those representations emerge from early retinotopic cortex, and crucially demonstrates that retinotopically tuned regions (LO-1/LO-2) are not necessarily constrained to retinotopic representations.


Assuntos
Percepção de Forma/fisiologia , Lobo Occipital/fisiologia , Retina/fisiologia , Córtex Visual/fisiologia , Campos Visuais/fisiologia , Vias Visuais/fisiologia , Adulto , Mapeamento Encefálico , Feminino , Humanos , Masculino , Análise Multivariada , Rede Nervosa/fisiologia , Reconhecimento Visual de Modelos/fisiologia
8.
J Vis ; 16(7): 17, 2016 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-27191945

RESUMO

Individual radial frequency (RF) patterns are generated by modulating a circle's radius as a sinusoidal function of polar angle and have been shown to tap into global shape processing mechanisms. Composite RF patterns can reproduce the complex outlines of natural shapes and examining these stimuli may allow us to interrogate global shape mechanisms that are recruited in biologically relevant tasks. We present evidence for a global shape aftereffect in a composite RF pattern stimulus comprising two RF components. Manipulations of the shape, location, size and spatial frequency of the stimuli revealed that this aftereffect could only be explained by the attenuation of intermediate-level global shape mechanisms. The tuning of the aftereffect to test stimulus size also revealed two mechanisms underlying the aftereffect; one that was tuned to size and one that was invariant. Finally, we show that these shape mechanisms may encode some RF information. However, the RF encoding we found was not capable of explaining the full extent of the aftereffect, indicating that encoding of other shape features such as curvature are also important in global shape processing.


Assuntos
Pós-Efeito de Figura/fisiologia , Percepção de Forma/fisiologia , Adaptação Fisiológica/fisiologia , Humanos , Reconhecimento Visual de Modelos/fisiologia , Estimulação Luminosa
9.
NPJ Precis Oncol ; 8(1): 122, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38806682

RESUMO

Interval breast cancers (IBCs) are cancers diagnosed between screening episodes. Understanding the biological differences between IBCs and screen-detected breast-cancers (SDBCs) has the potential to improve mammographic screening and patient management. We analysed and compared the genomic landscape of 288 IBCs and 473 SDBCs by whole genome sequencing of paired tumour-normal patient samples collected as part of the UK 100,000 Genomes Project. Compared to SDBCs, IBCs were more likely to be lobular, higher grade, and triple negative. A more aggressive clinical phenotype was reflected in IBCs displaying features of genomic instability including a higher mutation rate and number of chromosomal structural abnormalities, defective homologous recombination and TP53 mutations. We did not however, find evidence to indicate that IBCs are associated with a significantly different immune response. While IBCs do not represent a unique molecular class of invasive breast cancer they exhibit a more aggressive phenotype, which is likely to be a consequence of the timing of tumour initiation. This information is relevant both with respect to treatment as well as informing the screening interval for mammography.

10.
Psychol Trauma ; 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39235877

RESUMO

OBJECTIVE: Understanding judges' views is crucial to the successful adoption of a trauma-informed (TI) approach in the U.S. court system, yet little is known on this topic. We explored judges' attitudes of and experiences with TI practice to help fill this gap. METHOD: We surveyed 91 North Carolina district court judges, assessing their attitudes related to TI practice, use of trauma-informed practices (TIPs), previous trauma education, and support for different justice goals. We conducted independent-samples t tests and Poisson regression analyses to compare attitudes, use of TIPs, and education experiences between judges working in juvenile justice and those not in juvenile justice; descriptive statistics to examine rates of engagement with different TIPs; and bivariate correlation analyses to assess associations between TI practice outcomes and justice goals. RESULTS: Analyses revealed more favorable attitudes toward a TI approach and greater engagement with trauma education among judges working in juvenile versus adult courts; TIPs with the lowest levels of engagement related to policies and procedures; and strong positive correlations between favorable TI practice attitudes and support for rehabilitation and restoration. CONCLUSION: Findings highlight areas for growth in the movement to create more TI courts, such as strengthening support for TI practice in the adult criminal system and implementing TIPs related to policies, procedures, and outcomes, not just communication. Findings also support the connection between a TI approach and less punitive justice practices, signaling the potential role that TI judicial practice can play in shifting our legal system toward more transformative forms of justice. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

11.
Nat Commun ; 15(1): 5935, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-39009593

RESUMO

Clear cell renal cell carcinoma (ccRCC) is the most common form of kidney cancer, but a comprehensive description of its genomic landscape is lacking. We report the whole genome sequencing of 778 ccRCC patients enrolled in the 100,000 Genomes Project, providing for a detailed description of the somatic mutational landscape of ccRCC. We identify candidate driver genes, which as well as emphasising the major role of epigenetic regulation in ccRCC highlight additional biological pathways extending opportunities for therapeutic interventions. Genomic characterisation identified patients with divergent clinical outcome; higher number of structural copy number alterations associated with poorer prognosis, whereas VHL mutations were independently associated with a better prognosis. The observations that higher T-cell infiltration is associated with better overall survival and that genetically predicted immune evasion is not common supports the rationale for immunotherapy. These findings should inform personalised surveillance and treatment strategies for ccRCC patients.


Assuntos
Carcinoma de Células Renais , Neoplasias Renais , Mutação , Proteína Supressora de Tumor Von Hippel-Lindau , Sequenciamento Completo do Genoma , Carcinoma de Células Renais/genética , Carcinoma de Células Renais/terapia , Carcinoma de Células Renais/mortalidade , Carcinoma de Células Renais/patologia , Humanos , Neoplasias Renais/genética , Neoplasias Renais/terapia , Proteína Supressora de Tumor Von Hippel-Lindau/genética , Prognóstico , Masculino , Feminino , Variações do Número de Cópias de DNA , Pessoa de Meia-Idade , Epigênese Genética , Idoso , Regulação Neoplásica da Expressão Gênica , Imunoterapia/métodos
12.
Chem Commun (Camb) ; 59(51): 7923-7926, 2023 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-37278065

RESUMO

The reaction of alumylene [(Dippnacnac)Al] (1) with C60 fashions the first example of a structurally characterised aluminium-fulleride complex, [{(Dippnacnac)Al}3C60] (2), in which the Al centres are covalently bound to significantly elongated 6 : 6 bonds. Hydrolysis of 2 yields C60H6 and the reaction of 2 with [{Mesnacnac)Mg}2] cleaved off the Al fragments by affording the fulleride [{Mesnacnac)Mg}6C60].


Assuntos
Alumínio , Pentamidina , Hidrólise
13.
Clocks Sleep ; 4(4): 577-594, 2022 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-36278538

RESUMO

Light is an influential regulator of behavioural and physiological state in mammals. Features of cognitive performance such as memory, vigilance and alertness can be altered by bright light exposure under laboratory and field conditions. However, the importance of light as a regulator of performance in everyday life is hard to assess and has so far remained largely unclear. We set out to address this uncertainty by developing a tool to capture measures of cognitive performance and light exposure, at scale, and during everyday life. To this end, we generated an app (Brighter Time) which incorporated a psychomotor vigilance (PVT), an N-back and a visual search task with questionnaire-based assessments of demographic characteristics, general health, chronotype and sleep. The app also measured illuminance during task completion using the smartphone's intrinsic light meter. We undertook a pilot feasibility study of Brighter Time based on 91-week-long acquisition phases within a convenience sample (recruited by local advertisements and word of mouth) running Brighter Time on their own smartphones over two study phases in winter and summer. Study compliance was suitable (median = 20/21 requested task completions per subject). Statistically significant associations were observed between subjective sleepiness and performance in all tasks. Significant daily variations in PVT and visual search performance were also observed. Higher illuminance was associated with reduced reaction time and lower inverse efficiency score in the visual search. Brighter Time thus represents a viable option for large-scale collection of cognitive task data in everyday life, and is able to reveal associations between task performance and sleepiness, time of day and current illuminance. Brighter Time's utility could be extended to exploring associations with longer-term patterns of light exposure and/or other light metrics by integrating with wearable light meters.

14.
Brain Struct Funct ; 226(9): 2855-2867, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34529124

RESUMO

Macular degeneration (MD) causes central vision loss, removing input to corresponding representations in the primary visual cortex. There is disagreement concerning whether the cortical regions deprived of input can remain responsive, and the source of reported cortical responses is still debated. To simulate MD in controls, normally sighted participants viewed a bright central disk to adapt the retina, creating a transient 'retinal lesion' during a functional MRI experiment. Participants viewed blocks of faces, scrambled faces and uniform grey stimuli, either passively or whilst performing a one-back task. To assess the impact of the simulated lesion, participants repeated the paradigm using a more conventional mean luminance simulated scotoma without adaptation. Our results suggest our attempt to create a more realistic simulation of a lesion did not impact on responses in the representation of the simulated lesion. While most participants showed no evidence of stimulus-driven activation within the lesion representation, a few individuals (22%) exhibited responses similar to a participant with juvenile MD who completed the same paradigm (without adaptation). Reliability analysis showed that responses in the representation of the lesion were generally consistent irrespective of whether positive or negative. We provide some evidence that peripheral visual stimulation can also produce responses in central representations in controls while performing a task. This suggests that the 'signature of reorganization of visual processing', is not found solely in patients with retinal lesions, consistent with the idea that activity may be driven by unmasked top-down feedback.


Assuntos
Degeneração Macular , Retina , Córtex Visual , Humanos , Reprodutibilidade dos Testes , Retina/patologia , Retina/fisiopatologia , Escotoma , Córtex Visual/diagnóstico por imagem , Percepção Visual
15.
Elife ; 82019 05 07.
Artigo em Inglês | MEDLINE | ID: mdl-31063127

RESUMO

Recent developments in human neuroimaging make it possible to non-invasively measure neural activity from different cortical layers. This can potentially reveal not only which brain areas are engaged by a task, but also how. Specifically, bottom-up and top-down responses are associated with distinct laminar profiles. Here, we measured lamina-resolved fMRI responses during a visual task designed to induce concurrent bottom-up and top-down modulations via orthogonal manipulations of stimulus contrast and feature-based attention. BOLD responses were modulated by both stimulus contrast (bottom-up) and by engaging feature-based attention (top-down). Crucially, these effects operated at different cortical depths: Bottom-up modulations were strongest in the middle cortical layer and weaker in deep and superficial layers, while top-down modulations were strongest in the superficial layers. As such, we demonstrate that laminar activity profiles can discriminate between concurrent top-down and bottom-up processing, and are diagnostic of how a brain region is activated.


Assuntos
Córtex Visual/fisiologia , Percepção Visual , Adulto , Atenção , Feminino , Voluntários Saudáveis , Humanos , Imageamento por Ressonância Magnética , Masculino , Pessoa de Meia-Idade , Adulto Jovem
16.
Dalton Trans ; 48(45): 16936-16942, 2019 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-31687713

RESUMO

Ligand exchange reactions between combinations of the complexes [{(Arnacnac)Mg}2], where Ar = 2,6-iPr2C6H3 (Dip), 2,6-Et2C6H3 (Dep), 2,4,6-Me4C6H2 (Mes), and 2,6-Me2C6H3 (Xyl), [({Ph2P(NDip)2}Mg)2], [(Arnacnac)Li], where Ar = Mes or Xyl, and [{Ph2P(NDip)2}Li] were studied in deuterated aromatic and aliphatic solvents, and tetrahydrofuran. The reactions afforded product mixtures with asymmetrically substituted dimagnesium(i) complexes [(Arnacnac)MgMg(Ar'nacnac)], where Ar, Ar' = Dip, Dep, Mes, Xyl and [{Ph2P(NDip)2}MgMg(Arnacnac)], where Ar = Mes or Xyl, and suggest that the exchange of anionic ligands on the Mg22+ ion proceeds via an associative mechanism and is strongly dependent on ligand sterics and ligand shape, and can be very rapid. The activation reaction of fullerene C60 by dimagnesium(i) complexes [{(Arnacnac)Mg}2] and [({Ph2P(NDip)2}Mg)2] to fulleride complexes is similarly dependent on ligand sterics and ligand shape, but likely does not involve direct coordination of the fullerene to the Mg centre in dimagnesium(i) compounds prior to its reduction. The new C606- fulleride complex [({Ph2P(NDip)2}Mg)6C60] was prepared, and spectroscopically and structurally characterised.

17.
Chem Sci ; 10(46): 10755-10764, 2019 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-32055382

RESUMO

The reaction of the magnesium(i) complexes [{(Arnacnac)Mg}2], (Arnacnac = HC(MeCNAr)2, Ar = Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg} n C60], predominantly with n = 6, 4 and 2. 13C{1H} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(Arnacnac)Mg} n C60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [(Arnacnac)Mg]+ ions with C60 n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C60 6- ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+···C60 6- coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a central C60 6- anion and comparable frontier orbitals to C60 6- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(i) complexes.

18.
Curr Biol ; 28(21): 3435-3440.e4, 2018 11 05.
Artigo em Inglês | MEDLINE | ID: mdl-30344121

RESUMO

The human primary visual cortex (V1) is not only activated by incoming visual information but is also engaged by top-down cognitive processes, such as visual working memory, even in the absence of visual input [1-3]. This feedback may be critical to our ability to visualize specific visual features, as higher-order regions lack the selectivity to represent such information [4]. Clearly, such internally generated signals do not trigger genuine perception of the remembered stimulus, meaning they must be organized in a manner that is different to bottom-up-driven signals. Internally generated signals may be kept separate from incoming sensory data by virtue of the laminar organization of inter-area cortical connections. Namely, bottom-up driving connections target layer 4, located in the middle of the cortical column, and feedback connections target deep and superficial layers and avoid layer 4 [5-7]. Using lamina-resolved fMRI, we simultaneously measured the activity in three early visual cortical areas (V1-V3) that are recruited to represent stimulus information during visual working memory [8]. We observed item-specific working memory signals in early visual cortex. In V1, this item-specific activity was selectively present at deep and superficial cortical depths, avoiding the middle layers, and working-memory-related activity was present at all depths in V2 and V3. These results show for the first time the laminar organization of internally generated signals during visual working memory in the human visual system and provide new insights into how bottom-up and top-down signals in visual cortex are deployed.


Assuntos
Memória de Curto Prazo/fisiologia , Córtex Visual/fisiologia , Adulto , Feminino , Humanos , Imageamento por Ressonância Magnética , Masculino , Pessoa de Meia-Idade , Adulto Jovem
19.
Dalton Trans ; 46(48): 16872-16877, 2017 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-29188251

RESUMO

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L- = HC(Ph2P[double bond, length as m-dash]NDip)2-, Dip = 2,6-iPr2C6H3; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI24 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI25, prepared by iodination of LAlMe2, were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.

20.
Surgery ; 161(3): 846-854, 2017 03.
Artigo em Inglês | MEDLINE | ID: mdl-28029380

RESUMO

BACKGROUND: Minority-serving hospitals have greater readmission rates after operative procedures including colectomy; however, little is known about the contribution of hospital factors to readmission risk and mortality in this setting. This study evaluated the impact of hospital factors on readmissions and inpatient mortality after colorectal resections at minority-serving hospitals in the context of patient- and procedure-related factors. METHODS: More than 168,000 patients who underwent colorectal resections in 374 California hospitals (2004-2011) were analyzed using the State Inpatient Database and American Hospital Association Hospital Survey data. Sequential logistic regression analyses were performed to determine the associations between minority-serving hospital status and 30-day, 90-day, and repeated readmissions. RESULTS: Thirty-day, 90-day, and repeated readmission rates were 11.2%, 16.9%, and 2.9%, respectively. Odds for 30-day, 90-day, and repeated readmissions after colorectal resections were 19%, 20%, and 38% more likely at minority-serving hospitals versus non-minority-serving hospitals, respectively (P < .01), after controlling for age, sex, comorbidities, year, and procedure type. Patient factors accounted for up to 65% of the observed increase in odds for readmission at minority-serving hospitals while hospital-level factors contributed roughly 40%. Inpatient mortality was significantly greater at minority-serving hospitals versus non-minority-serving hospitals (4.9% vs 3.8%; P < .001). Risk factors significantly associated with readmissions and inpatient mortality included Medicaid/Medicare primary insurance, emergent operation, and ostomy creation. Low procedure volume was significantly associated with increased odds for inpatient mortality. CONCLUSION: Patient-level factors seemed to dominate the increased readmission risk after colorectal resections at minority-serving hospitals while hospital factors were less contributory. These findings need to be further validated to shape quality improvement interventions to decrease readmissions.


Assuntos
Colectomia/efeitos adversos , Neoplasias Colorretais/mortalidade , Neoplasias Colorretais/cirurgia , Grupos Minoritários/estatística & dados numéricos , Readmissão do Paciente/estatística & dados numéricos , Complicações Pós-Operatórias/mortalidade , Adolescente , Adulto , Idoso , California , Neoplasias Colorretais/etnologia , Feminino , Mortalidade Hospitalar , Humanos , Modelos Logísticos , Masculino , Pessoa de Meia-Idade , Complicações Pós-Operatórias/etnologia , Estudos Retrospectivos , Fatores de Risco , Adulto Jovem
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