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Metal nanoclusters (MNCs) represent a promising class of materials for catalytic carbon dioxide and proton reduction as well as dihydrogen oxidation. In such reactions, multiple proton-coupled electron transfer (PCET) processes are typically involved, and the current understanding of PCET mechanisms in MNCs has primarily focused on the sequential transfer mode. However, a concerted transfer pathway, i.e., concerted electron-proton transfer (CEPT), despite its potential for a higher catalytic rate and lower reaction barrier, still lacks comprehensive elucidation. Herein, we introduce an experimental paradigm to test the feasibility of the CEPT process in MNCs, by employing Au18(SR)14 (SR denotes thiolate ligand), Au22(SR)18, and Au25(SR)18- as model clusters. Detailed investigations indicate that the photoinduced PCET reactions in the designed system proceed via an CEPT pathway. Furthermore, the rate constants of gold nanoclusters (AuNCs) have been found to be correlated with both the size of the cluster and the flexibility of the Au-S framework. This newly identified PCET behavior in AuNCs is prominently different from that observed in semiconductor quantum dots and plasmonic metal nanoparticles. Our findings are of crucial importance for unveiling the catalytic mechanisms of quantum-confined metal nanomaterials and for the future rational design of more efficient catalysts.
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Selected gold complexes have been regarded as promising anti-cancer agents because they can bind with protein targets containing thiol or selenol moieties, but their clinical applications were hindered by the unbiased binding towards off-target thiol-proteins. Recently, a novel gold(III)-hydride complex (abbreviated as 1) with visible light-induced thiol reactivity has been reported as potent photo-activated anticancer agents (Angew. Chem. Int. Ed., 2020, 132, 11139). To explore new strategies to stimuli this potential antitumor drug, the effect of oriented external electric fields (OEEFs) on its geometric structure, electronic properties, and chemical reactivity was systematically investigated. Results reveal that imposing external electric fields along the Au-H bond of 1 can effectively activate this bond, which is conducive to its dissociation and the binding of Au site to potential targets. Hence, this study provides a new OEEF-strategy to activate this reported gold(III)-hydride, revealing its potential application in electrochemical therapy. We anticipate this work could promote the development of more electric field-activated anticancer agents. However, further experimental research should be conducted to verify the conclusions obtained in this work.
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Antineoplásicos , Oro , Oro/química , Antineoplásicos/química , Electricidad , Compuestos de SulfhidriloRESUMEN
The exploration of low-cost, efficient, environmentally safe, and selective catalysts for the activation of carbon-halogen bonds has become an important and challenging topic in modern chemistry. With the help of density functional theory (DFT), it is found that phenyl bromide (PhBr) can be efficiently chemisorbed by the Al12M (M = Be, Al, C, and P) superatoms via forming highly polarized Al-Br covalent bonds, where the C-Br bonds of PhBr can be effectively activated through the electron transfer from Al12M. The different electronic structures of these four Al12M superatoms pose a substantial effect on their performances on the activation of PhBr and the catalytic mechanisms of the Suzuki-Miyaura (SM) reaction. Among them, the alkali-metal-like superatom Al12P exhibits the best performance for the activation of PhBr. In particular, Al13 and Al12P with open-shell electronic structures exhibit catalytic performances comparable to those of previously reported catalysts for this coupling reaction. Hence, it is highly expected that Al13 and Al12P could be used as novel superatom catalysts for C-C coupling reactions and, therefore, open up new possibilities to use nonprecious superatoms in catalyzing the activation and transformation of carbon-halogen bonds.
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The unique characteristic of superatoms to show chemical properties like those of individual atoms opens a new avenue towards replacing noble metals as catalysts. Given the similar electronic structures of the ZrO superatom and the Pd atom, the CO oxidation mechanisms catalysed by (ZrO)n (n=1-4) clusters were investigated in detail to evaluate their catalytic performance. Our results reveal that a single ZrO superatom exhibits superior catalytic ability in CO oxidation than both larger (ZrO)n (n=2-4) clusters and a Pd atom, indicating the promising potential of ZrO as a "single-superatom catalyst". Moreover, the mechanism of CO oxidation catalysed by ZrO+/- suggests that depositing a ZrO superatom onto the electron-rich substrates is a better choice for practical catalysis application. Accordingly, a graphene nanosheet (coronene) was chosen as a representative substrate for ZrO and Pd to assess their catalytic performances in CO oxidation. Acting as an "electron sponge", this carbon substrate can both donate and accept charges in different reaction steps, enabling the supported ZrO to achieve enhanced catalytic performance in this process with a low energy barrier of 19.63â kcal/mol. This paper presents a new realization on the catalytic performance of Pd-like superatom in CO oxidation, which could increase the interests in exploring noble metal-like superatoms as efficient catalysts for various reactions.
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Catalytic conversion of N2O and CO into nonharmful gases is of great significance to reduce their adverse impact on the environment. The potential of the WSi12 superatom to serve as a new cluster catalyst for CO oxidation by N2O is examined for the first time. It is found that WSi12 prefers to adsorb the N2O molecule rather than the CO molecule, and the charge transfer from WSi12 to N2O results in the full activation of N2O into a physically absorbed N2 molecule and an activated oxygen atom that is attached to an edge of the hexagonal prism structure of WSi12. After the release of N2, the remaining oxygen atom can oxidize one CO molecule via overcoming a rate-limiting barrier of 28.19 kcal mol-1. By replacing the central W atom with Cr and Mo, the resulting MSi12 (M = Cr and Mo) superatoms exhibit catalytic performance for CO oxidation comparable to the parent WSi12. In particular, the catalytic ability of WSi12 for CO oxidation is well maintained when it is extended into tube-like WnSi6(n+1) (n = 2, 4, and 6) clusters with energy barriers of 25.63-29.50 kcal mol-1. Moreover, all these studied MSi12 (M = Cr, Mo, and W) and WnSi6(n+1) (n = 2, 4, and 6) species have high structural stability and can absorb sunlight to drive the catalytic process. This study not only opens a new door for the atomically precise design of new silicon-based nanoscale catalysts for various chemical reactions but also provides useful atomic-scale insights into the size effect of such catalysts in heterogeneous catalysis.
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BACKGROUND: The adaption of brain region is fundamental to the development and maintenance of nervous system disorders. The prelimbic cortex (PrL) participates in the affective components of the pain sensation. However, whether and how the adaptation of PrL contributes to the comorbidity of neuropathic pain and depression are unknown. METHODS: Using resting-state functional magnetic resonance imaging (rs-fMRI), genetic knockdown or overexpression, we systematically investigated the activity of PrL region in the pathogenesis of neuropathic pain/depression comorbid using the combined approaches of immunohistochemistry, electrophysiology, and behavior. RESULTS: The activity of PrL and the excitability of pyramidal neurons were decreased, and the osteoclastic tartrate-resistant acid phosphatase 5 (Acp5) expression in PrL neurons was upregulated following the acquisition of spared nerve injury (SNI)-induced comorbidity. Genetic knockdown of Acp5 in pyramidal neurons, but not parvalbumin (PV) neurons or somatostatin (SST) neurons, attenuated the decrease of spike number, depression-like behavior and mechanical allodynia in comorbidity rats. Overexpression of Acp5 in PrL pyramidal neurons decreased the spike number and induced the comorbid-like behavior in naïve rats. Moreover, the expression of interleukin-6 (IL-6), phosphorylated STAT3 (p-STAT3) and acetylated histone H3 (Ac-H3) were significantly increased following the acquisition of comorbidity in rats. Increased binding of STAT3 to the Acp5 gene promoter and the interaction between STAT3 and p300 enhanced acetylation of histone H3 and facilitated the transcription of Acp5 in PrL in the modeled rodents. Inhibition of IL-6/STAT3 pathway prevented the Acp5 upregulation and attenuated the comorbid-like behaviors in rats. CONCLUSIONS: These data suggest that the adaptation of PrL mediated by IL-6/STAT3/Acp5 pathway contributed to the comorbidity of neuropathic pain/depression induced by SNI.
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Interleucina-6 , Neuralgia , Fosfatasa Ácida/metabolismo , Animales , Comorbilidad , Depresión/metabolismo , Histonas , Interleucina-6/metabolismo , Neuralgia/metabolismo , Ratas , Factor de Transcripción STAT3/metabolismo , Fosfatasa Ácida Tartratorresistente/metabolismoRESUMEN
BACKGROUND: Currently, case studies or clinical trials in different patient populations remain the main resource underlying the understanding of disorder of consciousness (DoC). This provides a low efficacy for the derivation of data and the implementation of associated controlled experimental designs. Preclinical models provide precise controls, reduced variability, rich data output and limited ethical complexity. Nonhuman primates are suitable model animals for disorders of consciousness due to their brain structure being very similar to that of humans. Behavioral tests remain the primary standard for assessing the consciousness status of humans. However, there is currently no behavioral assessment scale available for evaluation of the state of consciousness disorder in nonhuman primates. This presents a significant challenge for the establishment of different models of consciousness disorder. Therefore, there is considerable motivation to focus on the development of a proper tool for assessment of the state of consciousness associated with nonhuman primate models that are based on clinically common consciousness assessment scales. METHODS: It is assumed that the Delphi and level analysis methods based on clinical consciousness disorder assessment scales may provide an effective way to select and include assessment indexes for levels of consciousness in nonhuman primates. RESULTS: 8 first-level indicators with 41 second-level indexes were selected preliminary as a pool of evaluation entries of state of consciousness of nonhuman primates. CONCLUSIONS: It may be practicable to extract appropriate indicators for non-human primates from the clinical consciousness disorder assessment scales. Besides, a combination of Delphi method, behavioral analysis, electroencephalography, neuroimaging (such as positron emission tomography-computed tomography) and functional magnetic resonance imaging is necessary to test the reliability and validity of the novel scale reported here.
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Trastornos de la Conciencia , Primates , Animales , Humanos , Trastornos de la Conciencia/diagnóstico , Reproducibilidad de los Resultados , Encéfalo/diagnóstico por imagen , Imagen por Resonancia MagnéticaRESUMEN
Developing efficient catalysts for the conversion of CO2 into fuels and value-added chemicals is of great significance to relieve the growing energy crisis and global warming. With the assistance of DFT calculations, it was found that, different from Al12 X (X=Be, Al, and C), the alkali-metal-like superatom Al12 P prefers to combine with CO2 via a bidentate double oxygen coordination, yielding a stable Al12 P(η2 -O2 C) complex containing an activated radical anion of CO2 (i.e., CO2 .- ). Thereby, this compound could not only participate in the subsequent cycloaddition reaction with propylene oxide but also initiate the radical reaction with hydrogen gas to form high-value chemicals, revealing that Al12 P can play an important role in catalyzing these conversion reactions. Considering that Al12 P has been produced in laboratory and is capable of absorbing visible light to drive the activation and transformation of CO2 , it is anticipated that this work could guide the discovery of additional superatom catalysts for CO2 transformation and open up a new research field of superatom catalysis.
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Converting earth-abundant nitrogen (N2) gas into ammonia (NH3) under mild conditions is one of the most important issues and a long-standing challenge in chemistry. Herein, a new superatom Ca3B was theoretically designed and characterized to reveal its catalytic performance in converting N2 into NH3 by means of density functional theory (DFT) computations. The alkali-metal-like identity of this cluster is verified by its lower vertical ionization energy (VIE, 4.29 eV) than that of potassium (4.34 eV), while its high stability was guaranteed by the large HOMO-LUMO gap and binding energy per atom (Eb). More importantly, this well-designed superatom possesses unique geometric and electronic features, which can fully activate N2via a "double-electron transfer" mechanism, and then convert the activated N2 into NH3 through a distal reaction pathway with a small energy barrier of 0.71 eV. It is optimistically hoped that this work could intrigue more endeavors to design specific superatoms as excellent catalysts for the chemical adsorption and reduction of N2 to NH3.
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Donor-linker-acceptor (D-L-A)-based photoinduced electron transfer (PET) has been frequently used for the construction of versatile fluorescent chemo/biosensors. However, sophisticated and tedious processes are generally required for the synthesis of these probes, which leads to poor design flexibility. In this work, by exploiting a Schiff base as a linker unit, a covalently bound D-L-A system was established and subsequently utilized for the development of a PET sensor. Cysteamine (Cys) and N-acetyl-l-cysteine (NAC) costabilized gold nanoclusters (Cys/NAC-AuNCs) were synthesized and adopted as an electron acceptor, and pyridoxal phosphate (PLP) was selected as an electron donor. PLP can form a Schiff base (an aldimine) with the primary amino group of Cys/NAC-AuNC through its aldehyde group and thereby suppresses the fluorescence of Cys/NAC-AuNC. The Rehm-Weller formula results and a HOMO-LUMO orbital study revealed that a reductive PET mechanism is responsible for the observed fluorescence quenching. Since the pyridoxal (PL) produced by the acid phosphatase (ACP)-catalyzed cleavage of PLP has a weak interaction with Cys/NAC-AuNC, a novel turn-on fluorescent method for selective detection of ACP was successfully realized. To the best of our knowledge, this is the first example of the development of a covalently bound D-L-A system for fluorescent PET sensing of enzyme activity based on AuNC nanoprobes using a Schiff base.
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Acetilcisteína/metabolismo , Cisteamina/metabolismo , Oro/metabolismo , Nanopartículas del Metal/química , Fosfato de Piridoxal/metabolismo , Acetilcisteína/química , Cisteamina/química , Teoría Funcional de la Densidad , Transporte de Electrón , Oro/química , Tamaño de la Partícula , Procesos Fotoquímicos , Fosfato de Piridoxal/química , Bases de Schiff/química , Bases de Schiff/metabolismo , Propiedades de SuperficieRESUMEN
The potential of the superalkali cation Li3+ for capturing N2 and its behavior in gaseous nitrogen have been theoretically studied at the MP2/6-311+G(d) level. The evolution of structures and stability of the Li3+(N2)n (n = 1-7) complexes shows that the N2 molecules tend to bind to different vertices of the Li3+ core, and that Li3+ might have the capacity to capture up to twelve nitrogen molecules in the first coordination shell. Based on natural population and molecular orbital analyses, Li3+ keeps its superatom identity in the lowest-lying Li3+(N2)n (n = 1-4) complexes. The change in the Gibbs free energies of possible fragmentation channels also indicates the thermodynamic stability of Li3+ in the (N2)n clusters when n ≤ 4. Different from the case of Li3+(H2O)n, where the electrostatic interaction is dominant, the electrostatic and polarization components are found to make nearly equal contributions to Li3+(N2)n complex formation. In addition, it can be concluded that the superalkali cation Li3+ surpasses heavy alkali metal cations in capturing N2 molecules, since it has a larger binding energy with N2 than Na+ and K+ ions.
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The possibility of using coinage metal atoms as excess electron acceptors is examined for the first time by designing a new class of M+-1-M'- (M = Li, Na, and K; M' = Cu, Ag, and Au) compounds termed "coinage metalides" on the basis of an intriguing Janus-type all-cis1,2,3,4,5,6-hexafluorocyclohexane (1) molecule. Under the large facial polarization of 1, the outermost ns1 electrons of alkali metal atoms can be transferred to coinage metal atoms, forming diffuse excess electrons around them. Consequently, the resulting M+-1-Cu- and M+-1-Ag- compounds exhibit significantly large nonlinear optical (NLO) responses. In particular, these novel M+-1-M'- compounds exhibit much higher stability (larger VIEs and Ec values) than that of the corresponding M+·1·M'- (M, M' = Li, Na, and K) alkalides. We hope this work could open up new possibilities for NLO material design by using coinage metal atoms as excess electron acceptors and, on the other hand, attract more experimental interest and efforts to synthesize such stable compounds in the laboratory.
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Superalkalis are clusters or molecules featuring lower ionization energies (IEs) than that of cesium atoms, and thus exhibit excellent reducing properties. Such special species have great potential to be used in the synthesis of unusual charge-transfer salts and cluster-assembled nanomaterials with tailored properties, in the reduction of carbon dioxide, or as hydrogen storage materials and noble-gas-trapping agents, etc. In this regard, ongoing efforts have been devoted to designing and characterizing superalkalis of new types. The recent progress on the study of superalkalis in terms of theoretical design, characterization, and potential application is summarized in this minireview. We hope this review will not only provide a broad overview of this research field, but also highlight the prospect of further extending the experimental synthesis and practical application of superalkalis.
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The potential application of the jellium model as guidance in the rational design of bimetallic superalkali cations is examined under gradient-corrected density functional theory for the first time. By using Li, Mg, and Al as atomic building blocks, a series of bimetallic cationic clusters with 2, 8, 20, and 40 valence electrons are obtained and investigated. As the corresponding neutral clusters tend to lose one valence electron to achieve closed-shell states in the jellium model, these studied cations exhibit much lower vertical electron affinities (EAvert , 3.42-4.95â eV) than the ionization energies (IEs) of alkali metal atoms, indicating their superalkali identities. The high stability of these cationic clusters is guaranteed by their considerable HOMO-LUMO gaps and binding energies per atom. Moreover, the feasibility of using the designed superalkalis as efficient reductants to activate CO2 and N2 molecules and as stable building blocks to assemble ionic superatom compounds is explored. Therefore, this study may provide an effective method for obtaining various metallic superatoms with extensive applications on the basis of the simple jellium rule.
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By substituting boron atoms for selected carbon atoms of a graphene quantum dot (GQD) model, namely a coronene molecule, the substituent effect on its geometric and electronic structure, as well as nonlinear optical response has been systemically investigated in theory. Our computations reveal that the boron substitution leads to a similar noncentrosymmetric apophysis structure for the boron-substituted coronene in singlet and triplet states. Noticeably, due to the small energy difference of 2.5â kcal mol-1 between the singlet and triplet states, the boron-substituted molecule can easily be switched between the antiferromagnetic (singlet state) and ferromagnetic (triplet state) state by slightly changing the external conditions. Notably, the boron-substituted coronene exhibits a considerably large first hyperpolarizability of 36241 au, because boron substitution yields a raised structure with an intermediate singlet diradical character. Hence, it is expected that this study not only provides new insights for the boron-substituent effect on the structure and properties of graphene but also may promote practical applications of GQDs in the fields of spintronics and nonlinear optics.
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Alkalides, as a representative kind of excess electron compounds, have been demonstrated to be potential nonlinear optical (NLO) materials with large static first hyperpolarizabilities (ß0). The possibility of utilizing coinage metal atoms as a novel excess electron source to design a series of alkalides, i.e., (M@36adz)M' (M = Cu, Ag, and Au; M' = Li, Na, and K), was examined by density functional theory calculations. The alkalide characteristics of these compounds are guaranteed by their HOMOs and VIE values as well as NBO analysis. In particular, all proposed alkalides exhibit considerable first hyperpolarizabilities (ß0) up to 61â¯590 au, indicating that they can be considered as novel NLO molecules of high performance. Moreover, a larger cage-complexant has been considered, and the resulting (Ag+@TriPip222)K- alkalide possesses a remarkably large ß0 value of 180â¯068 au. We hope that this work will provide a new recipe for designing excess electron compounds and, on the other hand, attract more research interest and efforts in exploring new, unconventional alkalides.
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Based on the density functional theory for exchange-correlation potential, fluorocarbon molecular cages are investigated as building blocks of hyperhalogens. By utilizing C8 F7 as a ligand, a series of hyperhalogen anions, that is, M(C8 F7 )2 (-) (M=Li, Na, and K) and M(C8 F7 )3 (-) (M=Be, Mg, and Ca), are modeled. Calculations show that all the C8 F7 moieties preserve their geometric and electronic integrity in these anions. These anionic molecules possess larger vertical electron detachment energies (5.11-6.45â eV) than that of C8 F7 (-) , verifying their hyperhalogen nature. Moreover, it is also revealed that using larger fluorinated cage C10 F9 as ligands can bring about hyperhalogen anions with larger vertical electron detachment energies. The stability of these studied anions is determined by their large HOMO-LUMO gaps and positive dissociation energies of predetermined possible fragmentation pathways. It is hoped this study will provide an approach for the construction of new types of hyperhalogens and stimulate more research in superatom chemistry.
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Guided by density functional theory (DFT) computations, a new series of superalkali-based alkalides, namely FLi2 (+) (aza222)K(-) , OLi3 (+) (aza222)K(-) , NLi4 (+) (aza222)K(-) , and Li3 (+) (aza222)K(-) were designed with various superalkali clusters embedded into an aza222 cage-complexant. These species possess diverse isomeric structures in which the encapsulated superalkalis preserve their identities and behave as alkali metal atoms. The results show that these novel alkalides possess larger complexation energies and enhanced hyperpolarizabilities (ß0 ) compared with alkali-metal-based and previous superalkali-based clusters. Especially, a prominent structural dependence of ß0 is observed for these studied compounds. Hence, the geometric factors that affect the nonlinear optical (NLO) response of such alkalides is elucidated in detail in this work. This study not only provides novel candidates for alkalides, it also offers an effective way to enhance the NLO response and stability of alkalides.
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Excess-electron compounds can be considered as novel candidates for nonlinear optical (NLO) materials because of their large static first hyperpolarizabilities (ß0 ). A room-temperature-stable, excess-electron compound, that is, the organic electride Na@(TriPip222), was successfully synthesized by the Dye group (J. Am. Chem. Soc. 2005, 127, 12416). In this work, the ß0 of this electride was first evaluated to be 1.13×106 â au, which revealed its potential as a high-performance NLO material. In particular, the substituent effects of different substituents on the structure, electride character, and NLO response of this electride were systemically studied for the first time by density functional theory calculations. The results revealed that the ß0 of Na@(TriPip222) could be further increased to 8.30×106 â au by introducing a fluoro substituent, whereas its NLO response completely disappeared if one nitryl group was introduced because the nitro-group substitution deprived the material of its electride identity. Moreover, herein the dependence of the NLO properties on the number of substituents and their relative positions was also detected in multifluoro-substituted Na@(TriPip222) compounds.
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The possibility of using superalkali clusters instead of alkali atoms as ligands to design a class of cationic compounds, referred to as hyperalkali cations, has been examined by using gradient-corrected density functional theory. By taking typical superalkalis (FLi2, OLi3, and NLi4) as examples, a series of hyperalkali cations ML2+ [M = (super)halogen; L = superalkali] have been constructed and investigated. Calculational results show that all the superalkali moieties preserve their geometric and electronic integrity in these proposed cations. The stability of these studied cations is guaranteed by the strong ionic bonds between superalkali ligand and (super)halogen core, as well as their large highest occupied molecular orbital-lowest unoccupied molecular orbital gaps and positive dissociation energies. In particular, all these proposed cations possess lower vertical electron affinities (2.36-3.56 eV) than those of their corresponding cationic superalkali ligands, verifying their hyperalkali nature. We, therefore, hope that this study will provide an approach to obtain new species with excellent reducing capability by utilizing various superalkalis as building blocks.