Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 215
Filtrar
Mais filtros

Base de dados
País/Região como assunto
Tipo de documento
Intervalo de ano de publicação
1.
Nat Mater ; 23(4): 570-576, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38297141

RESUMO

Soft building blocks, such as micelles, cells or soap bubbles, tend to adopt near-spherical geometry when densely packed together. As a result, their packing structures do not extend beyond those discovered in metallic glasses, quasicrystals and crystals. Here we report the emergence of two Frank-Kasper phases from the self-assembly of five-fold symmetric molecular pentagons. The µ phase, an important intermediate in superalloys, is indexed in soft matter, whereas the ϕ phase exhibits a structure distinct from known Frank-Kasper phases in metallic systems. We find a broad size and shape distribution of self-assembled mesoatoms formed by molecular pentagons while approaching equilibrium that contribute to the unique packing structures. This work provides insight into the manipulation of soft building blocks that deviate from the typical spherical geometry and opens avenues for the fabrication of 'soft alloy' structures that were previously unattainable in metal alloys.

2.
Acc Chem Res ; 57(8): 1111-1122, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38372967

RESUMO

ConspectusMolecular polyhedral cages, notable for their enclosed inner cavities, can possess varying degrees of symmetry, spanning from regular Platonic polyhedra to lower symmetry forms that may display chirality. Crafting chiral molecular cages typically involves using building blocks containing stereogenic elements or arranging achiral components in a manner that lacks mirror and inversion symmetries. Achieving precise control over their chirality poses both significance and challenges.In this Account, we present an overview of our research endeavors in the realm of chiral molecular polyhedral cages, drawing inspiration from Buckminster Fuller's "Face-Rotating Polyhedra (FRP)". Mathematically, FRP introduce a unique form of chirality distinguished by a rotating pattern around the center of each face, setting it apart from regular polyhedra.Molecular FRP can be constructed using two types of facial building blocks. The first includes rigid, planar molecules such as truxene and triazatruxene, which exhibit either clockwise or counterclockwise rotations in two dimensions. The second category involves propeller-like molecules, e.g., tetraphenylethylene, 1,2,3,4,5-penta(4-phenylaldehyde)pyrrole, and tridurylborane, displaying dynamic stereochemistry.The synthesis of FRP may potentially yield a diverse array of stereoisomers. Achieving high stereoselectivity becomes feasible through the selection of building blocks with specific substitution patterns and rigidity. Prominent noncovalent repulsive forces within the resulting cages often play a pivotal role in the dynamic covalent assembly process, ultimately leading to the formation of thermodynamically stable FRP products.The capacity to generate a multitude of stereoisomers, combined with the integration of chiral vertices, has facilitated investigations into phenomena such as chiral self-sorting and the "sergeant and soldiers" chiral amplification effect in FRP. Even the inclusion of one chiral vertex significantly impacts the stereochemical configuration of the entire cage. While many facial building blocks establish a stable rotational pattern in FRP, other units, such as tridurylborane, can dynamically transition between P and M configurations within the cage structures. The kinetic characteristics of such stereolabile FRP can be elucidated through physicochemical investigations.Our research extends beyond the FRP concept to encompass mathematical analysis of these structures. Graph theory, particularly the coloring problem, sheds light on the intricate facial patterns exhibited by various FRP stereoisomers and serves as an efficient tool to facilitate the discovery of novel FRP structures. This approach offers a fresh paradigm for designing and analyzing chiral molecular polyhedral cages, showcasing in our work the synergy between mathematics and molecular design.

3.
Chem Soc Rev ; 53(4): 1892-1914, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38230701

RESUMO

Molecular assembly is the process of organizing individual molecules into larger structures and complex systems. The self-assembly approach is predominantly utilized in creating artificial molecular assemblies, and was believed to be the primary mode of molecular assembly in living organisms as well. However, it has been shown that the assembly of many biological complexes is "catalysed" by other molecules, rather than relying solely on self-assembly. In this review, we summarize these catalysed-assembly (catassembly) phenomena in living organisms and systematically analyse their mechanisms. We then expand on these phenomena and discuss related concepts, including catalysed-disassembly and catalysed-reassembly. Catassembly proves to be an efficient and highly selective strategy for synergistically controlling and manipulating various noncovalent interactions, especially in hierarchical molecular assemblies. Overreliance on self-assembly may, to some extent, hinder the advancement of artificial molecular assembly with powerful features. Furthermore, inspired by the biological catassembly phenomena, we propose guidelines for designing artificial catassembly systems and developing characterization and theoretical methods, and review pioneering works along this new direction. Overall, this approach may broaden and deepen our understanding of molecular assembly, enabling the construction and control of intelligent assembly systems with advanced functionality.

4.
J Am Chem Soc ; 2024 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-39031612

RESUMO

In the realm of nanoscale materials design, achieving precise control over the dimensions of nanotubular architectures poses a substantial challenge. In our ongoing pursuit, we have successfully engineered a novel class of single-molecule nanotubes─isoreticular covalent organic pillars (iCOPs)─by stacking formylated macrocycles through multiple dynamic covalent imine bonds, guided by principles of reticular chemistry. Our strategic selection of rigid diamine linkers has facilitated the synthesis of a diverse array of iCOPs, each retaining a homologous structure yet offering distinct cavity shapes influenced by the linker choice. Notably, three of these iCOP variants feature continuous one-dimensional channels, exhibiting length-dependent host-guest interactions with α,ω-dibromoalkanes, and each presenting a distinct critical guest alkyl chain length threshold for efficient guest encapsulation. This newfound capability not only provides a platform for tailoring nanotubular structures with precision, but also opens new avenues for innovative applications in molecular recognition and the purification of complex mixtures.

5.
Small ; : e2402278, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38822712

RESUMO

The rapid proliferation of power sources equipped with lithium-ion batteries poses significant challenges in terms of post-scrap recycling and environmental impacts, necessitating urgent attention to the development of sustainable solutions. The cathode direct regeneration technologies present an optimal solution for the disposal of degraded cathodes, aiming to non-destructively re-lithiate and straightforwardly reuse degraded cathode materials with reasonable profits and excellent efficiency. Herein, a potential-regulated strategy is proposed for the direct recycling of degraded LiFePO4 cathodes, utilizing low-cost Na2SO3 as a reductant with lower redox potential in the alkaline systems. The aqueous re-lithiation approach, as a viable alternative, not only enables the re-lithiation of degraded cathode while ignoring variation in Li loss among different feedstocks but also utilizes the rapid sintering process to restore the cathode microstructure with desirable stoichiometry and crystallinity. The regenerated LiFePO4 exhibits enhanced electrochemical performance with a capacity of 144 mA h g-1 at 1 C and a high retention of 98% after 500 cycles at 5 C. Furthermore, this present work offers considerable prospects for the industrial implementation of directly recycled materials from lithium-ion batteries, resulting in improved economic benefits compared to conventional leaching methods.

6.
Langmuir ; 40(11): 5959-5967, 2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38449109

RESUMO

Iodine radioisotopes, produced or released during nuclear-related activities, severely affect human health and the environment. The efficient removal of radioiodine from both aqueous and vapor phases is crucial for the sustainable development of nuclear energy. In this study, we propose an "N-heteroatom engineering" strategy to design three porous organic cages with N-containing functional groups for efficient iodine capture. Among the molecular cages investigated, FT-Cage incorporating tertiary amine groups and RT-Cage with secondary amine groups show higher adsorption capacity and much faster iodine release compared to IT-Cage with imine groups. Detailed investigations demonstrate the superiority of amine groups, along with the influence of crystal structures and porosity, for iodine capture. These findings provide valuable insights for the design of porous organic cages with enhanced capabilities for capturing iodine.

7.
Clin Exp Rheumatol ; 2024 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-38530663

RESUMO

OBJECTIVES: To explore the effectiveness of tofacitinib for immunoglobulin G4-related disease (IgG4-RD) and idiopathic retroperitoneal fibrosis (IRF), and investigate the expression of JAKs in the lesion of these diseases. METHODS: Clinical data of patients with IgG4-RD or IRF who were administered with tofacitinib monotherapy were collected. IgG4-RD responder index (IgG4-RD RI) was assessed. The expression of JAK1, JAK2, JAK3, and TYK2 were analysed with immunohistochemistry staining in three salivary glands specimens of IgG4-RD and one retroperitoneal tissue of IRF. RESULTS: Two patients with IRF and two patients with IgG4-RD used tofacitinib monotherapy. Two patients with IRF achieved complete remission with diminished retroperitoneal mass and decreased CRP, as IgG4-RD RI decreased from 6 to 1 in both of them. One with IgG4-RD achieved complete remission with alleviated enlargement of pancreas and IgG4 level decreased from 13.7 g/L to 2.4 g/L, as IgG4-RD RI decreased from 12 to 1. One with IgG4-RD achieved partial response with IgG4 level decreased from 77.1g/L to 25.8g/L as IgG4-RD RI from 18 to 6. JAK1, JAK2, JAK3, and TYK2 expression were detected in biopsy tissues. The staining intensity of the JAK family on the lesion from one IRF patient was similar to those from IgG4-RD patients. CONCLUSIONS: Tofacitinib is a potentially effective treatment for IgG4-RD and IRF and it is reasonable to conduct clinical trial to validate its efficacy. The JAKs were expressed in the inflammatory lesions of IgG4-RD and IRF and they may share a common pathogenesis pathway that is independent of IgG4 production.

8.
Angew Chem Int Ed Engl ; 63(15): e202400467, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38273162

RESUMO

How Nature synthesizes enantiomerically pure substances from achiral or racemic resources remains a mystery. In this study, we aimed to emulate this natural phenomenon by constructing chiral tetrahedral cages through self-assembly, achieved by condensing two achiral compounds-a trisamine and a trisaldehyde. The occurrence of intercomponent CH⋅⋅⋅π interactions among the phenyl building blocks within the cage frameworks results in twisted conformations, imparting planar chirality to the tetrahedrons. In instances where the trisaldehyde precursor features electron-withdrawing ester side chains, we observed that the intermolecular CH⋅⋅⋅π forces are strong enough to prevent racemization. To attain enantioselective self-assembly, a chiral amine was introduced during the imine formation process. The addition of three equivalents of chiral amino mediator to one equivalent of the achiral trisaldehyde precursor formed a trisimino intermediate. This chiral compound was subsequently combined with the achiral trisamino precursor, leading to an imine exchange reaction that releasing the chiral amino mediator and formation of the tetrahedral cage with an enantiomeric excess (ee) of up to 75 %, exclusively composed of achiral building blocks. This experimental observation aligns with theoretical calculations based on the free energies of related cage structures. Moreover, since the chiral amine was not consumed during the imine exchange cycle, it enabled the enantioselective self-assembly of the tetrahedral cage for multiple cycles when new batches of the achiral trisaldehyde and trisamino precursors were successively added.

9.
Angew Chem Int Ed Engl ; 63(15): e202400172, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38345140

RESUMO

A negatively curved aza-nanographene (NG) containing two octagons was synthesized by a regioselective and stepwise cyclodehydrogenation procedure, in which a double aza[7]helicene was simultaneously formed as an intermediate. Their saddle-shaped structures with negative curvature were unambiguously confirmed by X-ray crystallography, thereby enabling the exploration of the structure-property relationship by photophysical, electrochemical and conformational studies. Moreover, the assembly of the octagon-embedded aza-NG with fullerenes was probed by fluorescence spectral titration, with record-high binding constants (Ka=9.5×103 M-1 with C60, Ka=3.7×104 M-1 with C70) found among reported negatively curved polycyclic aromatic compounds. The tight association of aza-NG with C60 was further elucidated by X-ray diffraction analysis of their co-crystal, which showed the formation of a 1 : 1 complex with substantial concave-convex interactions.

10.
J Am Chem Soc ; 145(32): 17795-17804, 2023 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-37527407

RESUMO

The manipulation of chirality in molecular entities that rapidly interconvert between enantiomeric forms is challenging, particularly at the supramolecular level. Advances in controlling such dynamic stereochemical systems offer opportunities to understand chiral symmetry breaking and homochirality. Herein, we report the synthesis of a face-rotating tetrahedron (FRT), an organic molecular cage composed of tridurylborane facial units that undergo stereomutations between enantiomeric trefoil propeller-like conformations. After resolution, we show that the racemization barrier of the enantiopure FRT can be regulated in situ through the reversible binding of fluoride anions onto the tridurylborane moieties. Furthermore, the addition of an enantiopure phenylethanol to the FRT can effectively induce chirality of the molecular cage by preferentially binding to one of its enantiomeric conformers. This study presents a new paradigm for controlling dynamic chirality in supramolecular systems, which may have implications for asymmetric synthesis and dynamic stereochemistry.

11.
Biomacromolecules ; 24(11): 5162-5174, 2023 11 13.
Artigo em Inglês | MEDLINE | ID: mdl-37889885

RESUMO

The alluring correlations of cellular behaviors with viscoelastic extracellular matrices have driven increasing endeavors directed toward the understanding of mechanical cues on cell growth and differentiation via preparing biomimetic scaffolds/gels with viscoelastic controllability. Indeed, systematic investigations, especially into calcium phosphate-containing biomimetics, are relatively rare. Here, oxidized hyaluronic acid/hydroxyapatite hybrids (OHAHs) were synthesized by hyaluronan-mediated biomimetic mineralization with confined ion diffusion and subsequent oxidization treatment. The collagen self-assembly was applied to fabricate tunable stress relaxing fibrillar matrices in the presence of OHAHs in which the incorporated hyaluronic acid with aldehyde groups acted to improve the component compatibility as well as to supplement the molecular interactions with the occurrence of a Schiff-base reaction. With the addition of varying OHAH contents, the self-assembly behavior of collagen was altered, and the obtained collagen-hybrid (CH) matrices presented a heterogeneous fibrillar structure interspersed with OHAHs, characterized by large fibrillar bundles coexisting with small fibrils. The OHAHs improved the hydrogel stability of pure collagen, and according to rheological and nanoindentation measurements, CH matrices also exhibited tunable stress relaxation rates, following an OHAH concentration-dependent fashion. The proliferation and spreading of MC3T3-E1 cells cultured onto such CH matrices were further found to increase with the stress relaxing rate of the matrices. The present study showed that the introduction of hydroxyapatite incorporated with active hyaluronic acid during collagen reconstitution was a simple and effective strategy to realize the preparation of tunable stress relaxing biomimetic matrices potentially used for further appraising the regulation of mechanical cues on cell behaviors.


Assuntos
Durapatita , Ácido Hialurônico , Ácido Hialurônico/química , Durapatita/química , Biomimética , Colágeno/química , Matriz Extracelular , Hidrogéis/química
12.
Phys Chem Chem Phys ; 25(16): 11530-11544, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37039422

RESUMO

Compared with monometallic selenides, bimetallic selenides have better synergistic effects and more abundant active sites for electrochemical reactions. As an important member of the transition metal oxide family, NiCoSe2 has been widely used in energy storage devices and has shown excellent electrochemical performance. So in this paper, nitrogen-doped carbon decorated NiCoSe2 composites (NiCoSe2/NC-700, NiCoSe2/NC-800, and NiCoSe2/NC-900) with a microflower structure were synthesized by calcining nickel-cobalt bimetallic organic skeleton materials at different temperatures, and were used as anode materials for rechargeable lithium-ion batteries. Because the MOF precursor has many advantages such as structural controllability, and a bimetal synergistic effect, the test results showed that the prepared NiCoSe2/NC composites have a special morphology, outstanding electrical conductivity, excellent lithium storage performance and electrochemical cycling performance in the process of being used as anode materials for lithium-ion batteries. The NiCoSe2/NC-800 materials displayed a high initial capacity (2099.8/1084.3 mA h g-1), and still maintained a high capacity (1041.2/989.9 mA h g-1) after 100 cycles at a current density of 0.1 A g-1 and in the voltage range of 0.01-3.0 V. In addition, at high current densities of 0.5 A g-1 and 1.0 A g-1, the increased capacity of NiCoSe2/NC composites may be due to the activation of electrodes and the pseudocapacitance during cycling. Through ex situ XRD experiments, the lithium storage mechanism of the NiCoSe2/NC-800 electrode material during cycling was further studied, and NiCoSe2/NC-800 was continuously converted into Ni, Co, and Li2Se during cycling.

13.
Phytother Res ; 37(12): 5700-5723, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37748788

RESUMO

Galangin is an important flavonoid with natural activity, that is abundant in galangal and propolis. Currently, various biological activities of galangin have been disclosed, including anti-inflammation, antibacterial effect, anti-oxidative stress and aging, anti-fibrosis, and antihypertensive effect. Based on the above bioactivities, more and more attention has been paid to the role of galangin in neurodegenerative diseases, rheumatoid arthritis, osteoarthritis, osteoporosis, skin diseases, and cancer. In this paper, the natural sources, pharmacokinetics, bioactivities, and therapeutic potential of galangin against various diseases were systematically reviewed by collecting and summarizing relevant literature. In addition, the molecular mechanism and new preparation of galangin in the treatment of related diseases are also discussed, to broaden the application prospect and provide reference for its clinical application. Furthermore, it should be noted that current toxicity and clinical studies of galangin are insufficient, and more evidence is needed to support its possibility as a functional food.


Assuntos
Flavonoides , Estresse Oxidativo , Flavonoides/farmacologia , Flavonoides/uso terapêutico
14.
Int J Mol Sci ; 24(19)2023 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-37833910

RESUMO

Both inosine and guanosine are precursors of uric acid that may cause the diseases of hyperuricemia and gout in humans. Here, a promising bacterial strain for efficiently biodegrading both inosine and guanosine was successfully isolated from a healthy human intestine and identified as Bacillus paranthracis YD01 with 16S rRNA analysis. An initial amount of 49.6 mg·L-1 of inosine or 49.9 mg·L-1 of guanosine was completely removed by YD01 within 12 h, which showed that YD01 had a strong ability to biodegrade inosine and guanosine. Furthermore, the initial amount of 49.2 mg·L-1 of inosine or 49.5 mg·L-1 of guanosine was totally catalyzed by the intracellular crude enzymes of YD01 within 6 h, and the initial inosine amount of 49.6 mg·L-1 or guanosine of 49.7 mg·L-1 was biodegraded by the extracellular crude enzymes of YD01 within 9 h. Illumina Hiseq sequencing and database gene annotation were used to elucidate the genomic characteristics of B. paranthracis YD01. Purine nucleoside phosphorylase, encoded by gene 1785, gene 3933, and gene 4403, was found in the KEEG database, which played a crucial role in the biodegradation of inosine and guanosine. The results of this study provide valuable insights into the mechanisms for biodegrading inosine and guanosine using B. paranthracis YD01.


Assuntos
Guanosina , Inosina , Humanos , Guanosina/metabolismo , RNA Ribossômico 16S/genética , Inosina/metabolismo , Purina-Núcleosídeo Fosforilase/metabolismo
15.
J Environ Sci (China) ; 124: 782-793, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36182183

RESUMO

Nitrated polycyclic aromatic hydrocarbons (NPAHs) are widespread organic pollutants that possess carcinogenic and mutagenic properties, so they may pose a risk to the environment and human health. In this study, the concentrations of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) in 30 surface water samples and 26 sediment samples were measured in 2018 from the Taige Canal, one of the main rivers flowing into Taihu Lake, China. The total NPAH concentrations in water and sediment ranged from 14.7 to 235 ng/L and 22.9 to 96.5 ng/g dw, respectively. 9-nitrophenanthrene (nd-76.3 ng/L) was the dominant compound in surface water, while 2+3-nitrofluoranthene (1.73-18.1 ng/g dw) dominated in sediment. Among PAHs, concentration ranging from 1,097 to 2,981 ng/L and 1,089 to 4,489 ng/g dw in surface water and sediment, respectively. There was a strong positive correlation between the log octanol-water partition coefficient (Kow) and log sediment-water partition coefficient due to hydrophobic interaction. The fugacity fraction value increased with the decrease of log Kow, and chrysene was transferred from water into sediment. The residual NPAHs in surface water and sediment of the Taige Canal have partial correlation. Diesel engine and coal combustion emissions were probably the principal sources of NPAHs in surface water and sediment. The results of ecological risk assessment showed that some NPAHs in water (e.g, 1-nitropyrene and 6-nitrochrysene) and sediment (e.g., 2-nitrobiphenyl, 5-nitroacenaphthene, 9-nitrophenanthrene and 2+3-nitrofluoranthene) had moderate ecological risks, which should be of concern.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , China , Crisenos/análise , Carvão Mineral/análise , Monitoramento Ambiental/métodos , Fluorenos , Sedimentos Geológicos/química , Humanos , Nitratos , Octanóis , Fenantrenos , Hidrocarbonetos Policíclicos Aromáticos/análise , Medição de Risco , Água , Poluentes Químicos da Água/análise
16.
Angew Chem Int Ed Engl ; 62(4): e202215367, 2023 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-36428269

RESUMO

Chiral nanographenes with both high fluorescence quantum yields (ΦF ) and large dissymmetry factors (glum ) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement of glum , whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with high ΦF by helical π-extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record high ΦF of 93 % among the reported chiral nanographenes and excellent CPL brightness (BCPL ) of 32 M-1 cm-1 .

17.
J Am Chem Soc ; 144(42): 19410-19416, 2022 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-36223688

RESUMO

Trace water in organic solvents can play a crucial role in the construction of supramolecular assemblies, which has not gained enough attention until very recent years. Herein, we demonstrate that residual water in organic solvents plays a decisive role in the regulation of the evolution of assembled structures and their functionality. By adding Mg(ClO4)2 into a multi-component organic solution containing terpyridine-based ligand 3Tpy and monodentate imidazole-based ligand M2, the system underwent an unexpected kinetic evolution. Metallo-supramolecular polymers (MSP) formed first by the coordination of 3Tpy and Mg2+, but they subsequently decomposed due to the interference of M2, resulting in a transient MSP system. Further investigation revealed that this occurred because residual water in the solvent and M2 cooperatively coordinated with Mg2+. This allowed M2 to capture Mg2+ from MSP, which led to depolymerization. However, owing to the slow reaction between trace water/M2/Mg2+, the formation of MSP still occurred first. Therefore, water regulated both the thermodynamics and kinetics of the system and was the key factor for constructing the transient MSP. Fine-tuning the water content and other assembly motifs regulated the assembly evolution pathway, tuned the MSP lifetime, and made the luminescent color of the system undergo intriguing transition processes over time.


Assuntos
Imidazóis , Água , Água/química , Ligantes , Solventes/química , Polímeros/química
18.
Small ; 18(12): e2107102, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35088521

RESUMO

Aqueous zinc-ion batteries (ZIBs) have recently attracted people's extensive attention in their application in energy storage systems resulting from their exclusive characteristics of low cost and environmental compatibility. However, finding suitable cathode materials continues to be the major challenge. Polyoxovanadates (POVs), as an important branch of polyoxometalates (POMs), are considered as a promising electrode material for reversible aqueous ZIBs relying on the flexible valence state of V. Herein, POVs (K2 Zn2 V10 O28 : KZVO) are reported as an advanced cathode for storing Zn2+ , which delivers a high discharge capacity of 223.4 mAh g-1 at 0.1 A g-1 , considerable energy density (182.9 Wh kg-1 ) and power density (40.38 W kg-1 ), and robust cyclic performance. In addition, the dynamic properties of the KZVO/Zn battery are revealed by pseudocapacitance analysis and GITT tests. Meanwhile, the storage mechanism of Zn2+ is further analyzed by ex situ XRD, XPS, TEM, and HRTEM. Overall, this work not only draws up a cathode material for the POMs system in aqueous ZIBs, but also demonstrates that POMs are the rising star in energy storage and electric energy applications.

19.
Chembiochem ; 23(23): e202200456, 2022 12 05.
Artigo em Inglês | MEDLINE | ID: mdl-36193860

RESUMO

We report the implementation of coordination complexes containing two types of cationic moieties, i. e. pyridinium and ammonium quaternary salt, as potential inhibitors of human cholinesterase enzymes. Utilization of ligands containing NNO-coordination site and binding zinc metal ion allowed mono- and tetra-nuclear complexes to be obtained with corner and grid structural type, respectively, thus affecting the overall charge of the compounds (from +1 to +8). We were able to examine for the first time the multivalency effect of metallosupramolecular species on their inhibitory abilities towards acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). Importantly, resolution of the crystal structures of the obtained enzyme-substrate complexes provided a better understanding of the inhibition process at the molecular level.


Assuntos
Acetilcolinesterase , Butirilcolinesterase , Humanos , Butirilcolinesterase/química , Butirilcolinesterase/metabolismo , Acetilcolinesterase/química , Inibidores da Colinesterase/farmacologia , Inibidores da Colinesterase/química , Ligantes , Cátions , Simulação de Acoplamento Molecular
20.
Chemistry ; 28(58): e202202243, 2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-35880725

RESUMO

We present here the synthesis and in-depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole-fused double helicene with the previously reported all-carbon and thiadiazole-fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from <1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole-fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin-related applications.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA