Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Valence self-regulation of sulfur in nanoclusters.

ABSTRACT: The valence self-regulation of sulfur from the "-2" valence state in thiols to the "-1" valence state in hydroxylated thiolates has been accomplished using the Pt1Ag28 nanocluster as a platform-the first time that the "-1" valent sulfur has been detected as S-1. Two previously unknown nanoclusters, Pt1Ag28(SR)20 and Pt1Ag28(SR)18(HO-SR)2 (where SR represents 2-adamantanethiol), have been synthesized and characterized-in the latter nanocluster, the presence of hydroxyl induces the valence regulation of two special S atoms from "-2" (in SR) to "-1" valence state in the HO-S(Ag)R. Because of the contrasting nature of the capping ligands in these two nanoclusters [i.e., only SR in Pt1Ag28(SR)20 or both SR- and HO-SR- in Pt1Ag28(SR)18(HO-SR)2], they exhibit differing shell architectures, even though their cores (Pt1Ag12) are in the same icosahedral configuration. Single-crystal x-ray diffraction analysis revealed their 1:1 cocrystallization, and mass spectrometry verified the presence of hydroxyls on Pt1Ag28(SR)18(HO-SR)2.

SUBMITTER: Kang X

PROVIDER: S-EPMC6874481 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Valence self-regulation of sulfur in nanoclusters.

Kang Xi X Xu Fengqing F Wei Xiao X Wang Shuxin S Zhu Manzhou M

Science advances 20191122 11

The valence self-regulation of sulfur from the "-2" valence state in thiols to the "-1" valence state in hydroxylated thiolates has been accomplished using the Pt1Ag28 nanocluster as a platform-the first time that the "-1" valent sulfur has been detected as S-1. Two previously unknown nanoclusters, Pt1Ag28(SR)20 and Pt1Ag28(SR)18(HO-SR)2 (where SR represents 2-adamantanethiol), have been ...[more]

PMID: 31803835

Similar Datasets

Core-dependent properties of copper nanoclusters: valence-pure nanoclusters as NIR TADF emitters and mixed-valence ones as semiconductors.

Project description:We report herein that copper alkynyl nanoclusters show metal-core dependent properties via a charge-transfer mechanism, which enables new understanding of their structure-property relationship. Initially, nanoclusters 1 and 2 bearing respective Cu(i)15 (C1) and Cu(i)28 (C2) cores were prepared and revealed to display near-infrared (NIR) photoluminescence mainly from the mixed alkynyl → Cu(i) ligand-to-metal charge transfer (LMCT) and cluster-centered transition, and they further exhibit thermally activated delayed fluorescence (TADF). Subsequently, a vanadate-induced oxidative approach to in situ generate a nucleating Cu(ii) cation led to assembly of 3 and 4 featuring respective [Cu(ii)O6]@Cu(i)47 (C3) and {[Cu(ii)O4]·[VO4]2}@Cu(i)46 (C4) cores. While interstitial occupancy of Cu(ii) triggers inter-valence charge-transfer (IVCT) from Cu(i) to Cu(ii) to quench the photoluminescence of 3 and 4, such a process facilitates charge mobility to render them semiconductive. Overall, metal-core modification results in an interplay between charge-transfer processes to switch TADF to semiconductivity, which underpins an unusual structure-property correlation for designed synthesis of metal nanoclusters with unique properties and functions.

| S-EPMC7003970 | biostudies-literature

Sulfur stabilizing metal nanoclusters on carbon at high temperatures.

Project description:Supported metal nanoclusters consisting of several dozen atoms are highly attractive for heterogeneous catalysis with unique catalytic properties. However, the metal nanocluster catalysts face the challenges of thermal sintering and consequent deactivation owing to the loss of metal surface areas particularly in the applications of high-temperature reactions. Here, we report that sulfur-a documented poison reagent for metal catalysts-when doped in a carbon matrix can stabilize ~1 nanometer metal nanoclusters (Pt, Ru, Rh, Os, and Ir) at high temperatures up to 700 °C. We find that the enhanced adhesion strength between metal nanoclusters and the sulfur-doped carbon support, which arises from the interfacial metal-sulfur bonding, greatly retards both metal atom diffusion and nanocluster migration. In catalyzing propane dehydrogenation at 550 °C, the sulfur-doped carbon supported Pt nanocluster catalyst with interfacial electronic effects exhibits higher selectivity to propene as well as more stable durability than sulfur-free carbon supported catalysts.

| S-EPMC8149400 | biostudies-literature

Hierarchical Micro-Nanoclusters of Bimetallic Layered Hydroxide Polyhedrons as Advanced Sulfur Reservoir for High-Performance Lithium-Sulfur Batteries.

Project description:Rational construction of sulfur electrodes is essential in pursuit of practically viable lithium-sulfur (Li-S) batteries. Herein, bimetallic NiCo-layered double hydroxide (NiCo-LDH) with a unique hierarchical micro-nano architecture is developed as an advanced sulfur reservoir for Li-S batteries. Compared with the monometallic Co-layered double hydroxide (Co-LDH) counterpart, the bimetallic configuration realizes much enriched, miniaturized, and vertically aligned LDH nanosheets assembled in hollow polyhedral nanoarchitecture, which geometrically benefits the interface exposure for host-guest interactions. Beyond that, the introduction of secondary metal intensifies the chemical interactions between layered double hydroxide (LDH) and sulfur species, which implements strong sulfur immobilization and catalyzation for rapid and durable sulfur electrochemistry. Furthermore, the favorable NiCo-LDH is architecturally upgraded into closely packed micro-nano clusters with facilitated long-range electron/ion conduction and robust structural integrity. Due to these attributes, the corresponding Li-S cells realize excellent cyclability over 800 cycles with a minimum capacity fading of 0.04% per cycle and good rate capability up to 2 C. Moreover, highly reversible areal capacity of 4.3 mAh cm-2 can be achieved under a raised sulfur loading of 5.5 mg cm-2. This work provides not only an effective architectural design but also a deepened understanding on bimetallic LDH sulfur reservoir for high-performance Li-S batteries.

| S-EPMC8025003 | biostudies-literature

DNA-enabled self-assembly of plasmonic nanoclusters.

Project description:DNA nanotechnology provides a versatile foundation for the chemical assembly of nanostructures. Plasmonic nanoparticle assemblies are of particular interest because they can be tailored to exhibit a broad range of electromagnetic phenomena. In this Letter, we report the assembly of DNA-functionalized nanoparticles into heteropentamer clusters, which consist of a smaller gold sphere surrounded by a ring of four larger spheres. Magnetic and Fano-like resonances are observed in individual clusters. The DNA plays a dual role: it selectively assembles the clusters in solution and functions as an insulating spacer between the conductive nanoparticles. These particle assemblies can be generalized to a new class of DNA-enabled plasmonic heterostructures that comprise various active and passive materials and other forms of DNA scaffolding.

| S-EPMC3478945 | biostudies-literature

Endurance Exercise Enhances Emotional Valence and Emotion Regulation.

Project description:Acute exercise consistently benefits both emotion and cognition, particularly cognitive control. We evaluated acute endurance exercise influences on emotion, domain-general cognitive control and the cognitive control of emotion, specifically cognitive reappraisal. Thirty-six endurance runners, defined as running at least 30 miles per week with one weekly run of at least 9 miles (21 female, age 18-30 years) participated. In a repeated measures design, participants walked at 57% age-adjusted maximum heart rate (HRmax; range 51%-63%) and ran at 70% HRmax (range 64%-76%) for 90 min on two separate days. Participants completed measures of emotional state and the Stroop test of domain-general cognitive control before, every 30 min during and 30 min after exercise. Participants also completed a cognitive reappraisal task (CRT) after exercise. Functional near-infrared spectroscopy (fNIRS) tracked changes in oxygenated and deoxygenated hemoglobin (O2Hb and dHb) levels in the prefrontal cortex (PFC). Results suggest that even at relatively moderate intensities, endurance athletes benefit emotionally from running both during and after exercise and task-related PFC oxygenation reductions do not appear to hinder prefrontal-dependent cognitive control.

| S-EPMC6232759 | biostudies-literature

Metal-sulfur valence orbital interaction energies in metal-dithiolene complexes: determination of charge and overlap interaction energies by comparison of core and valence ionization energy shifts.

Project description:The electronic interactions between metals and dithiolenes are important in the biological processes of many metalloenzymes as well as in diverse chemical and material applications. Of special note is the ability of the dithiolene ligand to support metal centers in multiple coordination environments and oxidation states. To better understand the nature of metal-dithiolene electronic interactions, new capabilities in gas-phase core photoelectron spectroscopy for molecules with high sublimation temperatures have been developed and applied to a series of molecules of the type Cp(2)M(bdt) (Cp = ?(5)-cyclopentadienyl, M = Ti, V, Mo, and bdt = benzenedithiolato). Comparison of the gas-phase core and valence ionization energy shifts provides a unique quantitative energy measure of valence orbital overlap interactions between the metal and the sulfur orbitals that is separated from the effects of charge redistribution. The results explain the large amount of sulfur character in the redox-active orbitals and the 'leveling' of oxidation state energies in metal-dithiolene systems. The experimentally determined orbital interaction energies reveal a previously unidentified overlap interaction of the predominantly sulfur HOMO of the bdt ligand with filled ? orbitals of the Cp ligands, suggesting that direct dithiolene interactions with other ligands bound to the metal could be significant for other metal-dithiolene systems in chemistry and biology.

| S-EPMC3205315 | biostudies-literature

Virus-templated plasmonic nanoclusters with icosahedral symmetry via directed self-assembly.

Project description:The assembly of plasmonic nanoparticles with precise spatial and orientational order may lead to structures with new electromagnetic properties at optical frequencies. The directed self-assembly method presented controls the interparticle-spacing and symmetry of the resulting nanometer-sized elements in solution. The self-assembly of three-dimensional (3D), icosahedral plasmonic nanosclusters (NCs) with resonances at visible wavelengths is demonstrated experimentally. The ideal NCs consist of twelve gold (Au) nanospheres (NSs) attached to thiol groups at predefined locations on the surface of a genetically engineered cowpea mosaic virus with icosahedral symmetry. In situ dynamic light scattering (DLS) measurements confirm the NSs assembly on the virus. Transmission electron micrographs (TEM) demonstrate the ability of the self-assembly method to control the nanoscopic symmetry of the bound NSs, which reflects the icosahedral symmetry of the virus. Both, TEM and DLS show that the NCs comprise of a distribution of capsids mostly covered (i.e., 6-12 NS/capsid) with NSs. 3D finite-element simulations of aqueous suspensions of NCs reproduce the experimental bulk absorbance measurements and major features of the spectra. Simulations results show that the fully assembled NCs give rise to a 10-fold surface-averaged enhancement of the local electromagnetic field.

| S-EPMC4283761 | biostudies-literature

Structural order enhances charge carrier transport in self-assembled Au-nanoclusters.

Project description:The collective properties of self-assembled nanoparticles with long-range order bear immense potential for customized electronic materials by design. However, to mitigate the shortcoming of the finite-size distribution of nanoparticles and thus, the inherent energetic disorder within assemblies, atomically precise nanoclusters are the most promising building blocks. We report an easy and broadly applicable method for the controlled self-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters into micro-crystals. This enables the determination of emergent optoelectronic properties which resulted from long-range order in such assemblies. Compared to the same nanoclusters in glassy, polycrystalline ensembles, we find a 100-fold increase in the electric conductivity and charge carrier mobility as well as additional optical transitions. We show that these effects are due to a vanishing energetic disorder and a drastically reduced activation energy to charge transport in the highly ordered assemblies. This first correlation of structure and electronic properties by comparing glassy and crystalline self-assembled superstructures of atomically precise gold nanoclusters paves the way towards functional materials with novel collective optoelectronic properties.

| S-EPMC7713068 | biostudies-literature

Arousal, valence, and the uncanny valley: psychophysiological and self-report findings.

Project description:The main prediction of the Uncanny Valley Hypothesis (UVH) is that observation of humanlike characters that are difficult to distinguish from the human counterpart will evoke a state of negative affect. Well-established electrophysiological [late positive potential (LPP) and facial electromyography (EMG)] and self-report [Self-Assessment Manikin (SAM)] indices of valence and arousal, i.e., the primary orthogonal dimensions of affective experience, were used to test this prediction by examining affective experience in response to categorically ambiguous compared with unambiguous avatar and human faces (N = 30). LPP and EMG provided direct psychophysiological indices of affective state during passive observation and the SAM provided self-reported indices of affective state during explicit cognitive evaluation of static facial stimuli. The faces were drawn from well-controlled morph continua representing the UVH' dimension of human likeness (DHL). The results provide no support for the notion that category ambiguity along the DHL is specifically associated with enhanced experience of negative affect. On the contrary, the LPP and SAM-based measures of arousal and valence indicated a general increase in negative affective state (i.e., enhanced arousal and negative valence) with greater morph distance from the human end of the DHL. A second sample (N = 30) produced the same finding, using an ad hoc self-rating scale of feelings of familiarity, i.e., an oft-used measure of affective experience along the UVH' familiarity dimension. In conclusion, this multi-method approach using well-validated psychophysiological and self-rating indices of arousal and valence rejects - for passive observation and for explicit affective evaluation of static faces - the main prediction of the UVH.

| S-EPMC4502535 | biostudies-literature

Oxytocin facilitates valence-dependent valuation of social evaluation of the self.

Project description:People are eager to know the self in other's eyes even with personal costs. However, what drives people costly to know evaluations remains unknown. Here we tested the hypothesis of placing subjective value on knowing social evaluations. To quantify the subjective value, we developed a pay-to-know choice task where individuals trade off profits against knowing social evaluations. Individuals computed independent unknown aversion towards positive and negative social evaluations and placed higher values on knowing social evaluation on positive than negative aspects. Such a valence-dependent valuation of social evaluation was facilitated by oxytocin, a neuropeptide linked to feedback learning and valuation processes, by decreasing values of negative social evaluation. Moreover, individuals scoring high in depression undervalued positive social evaluation, which was normalized by oxytocin. We reveal the psychological and computational processes underlying self-image formation/update and suggest a role of oxytocin in normalizing hypo-valuation of positive social evaluation in depression.

| S-EPMC7426917 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data