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1.
Nat Commun ; 12(1): 6186, 2021 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-34702816

RESUMO

Although the hollow icosahedral M12 kernel has been extensively observed in metal nanoclusters, its origin remains a mystery. Here we report a reasonable avenue for the generation of the hollow icosahedron: the kernel collapse from several small nano-building blocks to an integrated hollow icosahedron. On the basis of the Au alloying processes from Ag28Cu12(SR)24 to the template-maintained AuxAg28-xCu12(SR)24 and then to the template-transformed Au12CuyAg32-y(SR)30, the kernel evolution/collapse from "tetrahedral Ag4 + 4∗Ag3" to "tetrahedral Au4 + 4∗M3 (M = Au/Ag)" and then to "hollow icosahedral Au12" is mapped out. Significantly, the "kernel collapse" from small-sized nano-building blocks to large-sized nanostructures not only unveils the formation of hollow icosahedral M12 in this work, but also might be a very common approach in constructing metallic kernels of nanoclusters and nanoparticles (not limited to the M12 structure).

2.
Chemistry ; 2021 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-34643967

RESUMO

The [Aux Ag16-x (SAdm)8 (Dppe)2 ] nanocluster with aggregation-induced emission (AIE) was synthesized from a non-fluorescent [Au9 Ag12 (SAdm)4 (Dppm)6 Cl6 ](SbF6 )3 nanocluster via a ligand-exchange engineering (Dppe=1,2-Bis(diphenylphosphino)ethane, Dppm=Bis(diphenylphosphino)methane, HSAdm=1-Adamantanethiol). The nanocluster has a Au-doped icosahedral Aux Ag13-x core, capped by two Ag(SR)3 , one Ag(SR)2 and two Dppe ligands. By changing the achiral Dppe ligand into a chiral dbpb ligand ((2S,3S)-(-)-Bis(diphenylphosphino)butane or (2R,3R)-(+)-2,3-Bis(diphenylphosphino)butane), chiral nanoclusters are obtained. ESI-MS and UV-vis spectroscopy were performed to track the reaction. This work provides guidance for the construction of new clusters by etching clusters with multidentate phosphine ligands.

3.
Nanoscale ; 13(40): 17162-17167, 2021 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-34636384

RESUMO

Although several approaches have been exploited to trigger the structural transformation of metal nanoclusters, most cases are assigned to the unidirectional conversion, while the reversible conversion of nanoclusters remains challenging. In this work, the reversible conversion between two Au-Ag alloy nanoclusters, Au14Ag8(Dppm)6(CN)4Cl4 and Au14Ag4(Dppm)6Cl4, has been accomplished, which was tracked by UV-vis and ESI-MS spectroscopy. The condition of the nanocluster reversible conversion has been meticulously mapped out. Our results provide some new insights into the cluster transformation, which will benefit the future preparation of metalloid clusters with customized structures and properties.

4.
Nanomaterials (Basel) ; 11(10)2021 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-34685097

RESUMO

Surface modification has served as an efficient approach to dictate nanocluster structures and properties. In this work, based on an Ag22 nanocluster template, the effects of surface modification on intracluster constructions and intercluster packing modes, as well as the properties of nanoclusters or cluster-based crystallographic assemblies have been investigated. On the molecular level, the Ag22 nanocluster with larger surface steric hindrance was inclined to absorb more small-steric chlorine but less bulky thiol ligands on its surface. On the supramolecular level, the regulation of intramolecular and intermolecular interactions in nanocluster crystallographic assemblies rendered them CIEE (crystallization-induced emission enhancement)-active or -inactive nanomaterials. This study has some innovation in the molecular and intramolecular tailoring of metal nanoclusters, which is significant for the preparation of new cluster-based nanomaterials with customized structures and enhanced performances.

5.
Natl Sci Rev ; 8(3): nwaa077, 2021 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-34691583

RESUMO

The supramolecular chemistry of nanoclusters is a flourishing area of nano-research; however, the controllable assembly of cluster nano-building blocks in different arrays remains challenging. In this work, we report the hierarchical structural complexity of atomically precise nanoclusters in micrometric linear chains (1D array), grid networks (2D array) and superstructures (3D array). In the crystal lattice, the Ag29(SSR)12(PPh3)4 nanoclusters can be viewed as unassembled cluster dots (Ag29-0D). In the presence of Cs+ cations, the Ag29(SSR)12 nano-building blocks are selectively assembled into distinct arrays with different oxygen-carrying solvent molecules-Cs@Ag29(SSR)12(DMF) x as 1D linear chains (Ag29-1D), Cs@Ag29(SSR)12(NMP) x as 2D grid networks (Ag29-2D), and Cs@Ag29(SSR)12(TMS) x as 3D superstructures (Ag29-3D). Such self-assemblies of these Ag29(SSR)12 units have not only been observed in their crystalline state, but also in their amorphous state. Due to the diverse surface structures and crystalline packing modes, these Ag29-based assemblies manifest distinguishable optical absorptions and emissions in both solutions and crystallized films. Furthermore, the surface areas of the nanocluster crystals are evaluated, the maximum value of which occurs when the cluster nano-building blocks are assembled into 2D arrays (i.e. Ag29-2D). Overall, this work presents an exciting example of the hierarchical assembly of atomically precise nanoclusters by simply controlling the adsorbed molecules on the cluster surface.

6.
Inorg Chem ; 60(19): 14803-14809, 2021 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-34516083

RESUMO

Cl atoms can serve as the innermost core, the peripheral ligand, or the counterions of metal nanoclusters. Herein, we report the structural determination a Cl-enriched [Ag52(SAdm)31Cl13]2+. The ratio of Cl to AdmSH is quite high compared to those of other nanoclusters. Structurally, nine Cl atoms, existing at the interlayer of the inner kernel and the surface motif, serve as the bridging ligands to sustain the robustness of the whole structure. Interestingly, four Cl atoms on the motif structure can be substituted by Br. This work allows us to clear the regulation of Cl ligands in the structural construction of metal nanoclusters.

7.
Chem Commun (Camb) ; 57(80): 10383-10386, 2021 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-34542129

RESUMO

An intermediate-sized atomically precise metalloid silver nanocluster [Ag71(SR)31(Dppm)](SbF6)2 (Dppm = bis (diphenylphosphino)methane, SR = S-tBu) is reported, which comprises one building block Ag64, six SR5 pentagons, one sole SR ligand, a DppmAg2 handle, and an Ag5 lid. Structurally, a decahedron Ag23 kernel is observed in the metalloid silver nanocluster. Moreover, the Ag64 unit provides insights into the growth of large clusters such as Ag136(SR)64Cl3 and Ag141(SR)40Br12via assembly. The observed decahedron Ag23 provides a deeper understanding on Marks decahedron in larger nanoclusters, and the [Ag71(S-tBu)31(Dppm)](SbF6)2 uses Ag64 as a building block to predict the structure of larger metalloid nanoclusters.

8.
Nanoscale Horiz ; 6(11): 913-917, 2021 10 25.
Artigo em Inglês | MEDLINE | ID: mdl-34486633

RESUMO

The hierarchical assemblies of well-defined structural nanoclusters can help to better understand those of biologically important molecules such as DNA and proteins. Herein, we disclose the synthesis and characterization of a new silver nanocluster, that is Ag70(SR)42(PPh3)5 (Ag70-TPP). Directed by the ligands, Ag70-TPP nanoclusters undergo self-hierarchical assembly into a highly space-efficient complex secondary structure of a double helical 4H (DH4H) close packing pattern. The chirality of Ag70-TPP, and the van der Waals forces interactions between the ligands are believed to drive its DH4H arrangement, and the observed interlocking of the phosphine ligands of adjacent Ag70-TPP nanoclusters also contributed. Overall, this work has yielded important and unprecedented insights into the internal structure and crystallographic arrangement of nanoclusters.


Assuntos
Nanopartículas Metálicas , DNA , Ligantes , Proteínas , Prata
9.
Chem Sci ; 12(33): 11080-11088, 2021 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-34522305

RESUMO

The polarization effect has been a powerful tool in controlling the morphology of metal nanoparticles. However, a precise investigation of the polarization effect has been a challenging pursuit for a long time, and little has been achieved for analysis at the atomic level. Here the atomic-level analysis of the polarization effect in controlling the morphologies of metal nanoclusters is reported. By simply regulating the counterions, the controllable transformation from Pt1Ag28(S-PhMe2) x (S-Adm)18-x (PPh3)4 (x = 0-6, Pt1Ag28-2) to Pt1Ag24(S-PhMe2)18 (Pt1Ag24) with a spherical configuration or to Pt1Ag28(S-Adm)18(PPh3)4 (Pt1Ag28-1) with a tetrahedral configuration has been accomplished. In addition, the spherical or tetrahedral configuration of the clusters could be reversibly transformed by re-regulating the proportion of counterions with opposite charges. More significantly, the configuration transformation rate has been meticulously manipulated by regulating the polarization effect of the ions on the parent nanoclusters. The observations in this paper provide an intriguing nanomodel that enables the polarization effect to be understood at the atomic level.

10.
J Am Chem Soc ; 143(37): 15224-15232, 2021 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-34498861

RESUMO

Atomically precise noble metal nanoclusters provide a critical benchmark for the fundamental research of the origin of condensed matter because they retain the original state of the metal bonds. Also, knowledge about the transition from organometallic complexes to a nanoclusters is important for understanding the structural evolution of the nanoclusters, particularly their nucleation mechanism. Herein, three transition-size gold nanoclusters are prepared via a controlled diphosphine-mediated top-down routine. Starting from small-size nanoclusters, three new nanoclusters including Au13(SAdm)8(L4)2(BPh4) (Au13), Au14(S-c-C6H11)10L4 (Au14), and Au16(S-c-C6H11)11LPh* (Au16) are obtained by controlled clipping on the surface and kernel of initial nanoclusters. Combining their atomically precise structures with DFT theoretical calculations, the overall atom-by-atom structural evolution process from Au12(SR)12 (0 e-) to Au18(SR)14 (4 e-) is mapped out. In addition, studies on their electronic structures show that the evolution from an organometallic complex to nanoclusters is accompanied by a dramatic decrease in the HOMO-LUMO gaps. Most importantly, the formation of the first Au-Au bond is captured in the "Au4S4 to Au5" nucleation process from Au12(SR)12 complex to the Au13 nanocluster. This work provides a deep insight into the origin of inner core in Au NCs and their structural transition relationship with metal complexes.

11.
Chem Asian J ; 16(19): 2973-2977, 2021 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-34374215

RESUMO

The change in the valence state of nanocluster can induce remarkable changes in the properties and structure. However, achieving the valence state changes in nanoclusters is still a challenge. In this work, we use Cu2+ as dopant to "oxidize" [Ag62 S12 (SBut )32 ]2+ (4 free electrons) to obtain the new nanocluster: [Ag62-x Cux S12 (SBut )32 ]4+ with 2 free electrons. As revealed by its structure, the [Ag62-x Cux S12 (SBut )32 ]4+ (x=10∼21) has a similar structure to that of [Ag62 S12 (SBut )32 ]2+ precursor and all the Cu atoms occupy the surface site of nanocluster. It's worth noting that with the Cu atoms doping, the [Ag62-x Cux S12 (SBut )32 ]4+ nanocluster is more stable than [Ag62 S12 (SBut )32 ]2+ at higher temperature and in electrochemical cycle. This result has laid a foundation for the subsequent application and exploration. Overall, this work reveals crystals structure of a new Ag-Cu nanocluster and offers a new insight into the electron reduction/oxidation of nanocluster.

12.
Chem Commun (Camb) ; 57(70): 8774-8777, 2021 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-34378573

RESUMO

Alloying is one of the most effective strategies to change the properties of inorganic-organic hybrid materials, but there are few reports of the alloying of one-dimensional nanowires with precise atomic structure due to the difficulties in obtaining the single crystals of nanowires themselves. Herein, we describe the synthesis and characterization of an alloyed one-dimensional Ag-Cu nanowire [Ag2.5Cu1.5(S-Adm)4]n. Compared with the unalloyed [Ag4(S-Adm)4]n, our novel alloyed nanowire exhibits good conductivity, and its resistivity (as a powder) was determined to be 107 Ω m by impedance analysis-consistent with that of a semiconductor. Accordingly, based on these properties combined with its excellent thermal stability and high-yielding, gram-scale synthesis, [Ag2.5Cu1.5(S-Adm)4]n is proposed for electronic-device applications.

13.
J Chem Phys ; 154(18): 184302, 2021 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-34241021

RESUMO

The structure/composition of nanoclusters has a decisive influence on their physicochemical properties. In this work, we obtained two different Au-Ag nanoclusters, [Au9Ag12(SAdm)4(dppm)6Cl6]3+ and Au11Ag6(dppm)4(SAdm)4(CN)4, via controlling the Au/Ag molar ratios by a one-pot synthetic approach. The structure of nanoclusters was confirmed and testified by single-crystal x-ray diffraction, electrospray ionization time-of-flight mass spectrometry, XPS, powder x-ray diffraction, and electron paramagnetic resonance. The Au11Ag6 nanocluster possessed a M13 core caped by four Au atoms and four dppm and four AdmS ligands. Interestingly, four CN are observed to locate at the equator of the M13 core. Both nanoclusters contain a similar icosahedral M13 core, whereas their surface structures are totally different. However, the Au11Ag6 nanocluster exhibits good stability and strong red photoluminescence in solution.

14.
Dalton Trans ; 50(29): 10113-10118, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34251382

RESUMO

Herein, density functional theory (DFT) calculations were performed to elucidate the mechanism of the reversible single atom size conversion between [Au10(DMPP)4(C6H11C[triple bond, length as m-dash]C)]3+ and [Au9(DMPP)4]3+ (DMPP is 2,2'-bis-(dimethylphosphino)-1,1'-biphenyl, the simplified, theoretical model of the experimentally used 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl). The presence of a unique alkyne group is pivotal to the nucleophilic attack of the phosphine ligand on the electron-deficient Au10 core. After that, a formal ligand exchange and facile 1,2-P (of the diphosphine ligand) transfer occur to generate the Au9 cluster product. By contrast, the absence of the alkyne group results in a relatively electron-rich Au9 core, and thus an electrophilic attack of the Au(alkyne) complex on the most electron-rich metal sites occurs first. After that, the Au(alkyne) migration on the cluster surface, 1,2-P transfer and core-reconstruction occur successively to generate the thermodynamically highly stable Au10 cluster product.

15.
Inorg Chem ; 60(15): 11640-11647, 2021 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-34286977

RESUMO

The structural determination of alloy hydride nanoclusters with high nuclearity remains challenging. We herein report the synthetic procedure and the structural elucidation of an Au-Ag alloy nanocluster with 12 hydride ligands-[Au16Ag43H12(SPhCl2)34]5-. The structure of [Au16Ag43H12(SPhCl2)34]5- comprises an Au16Ag3 kernel that is stabilized by 12 hydride ligands, 8 thiol bridges, and 6 Agm(SR)n motif units. The 12 hydride ligands in Au16Ag43 have been confirmed by both 2H NMR and ESI-MS measurements, and their positions have been theoretically evaluated, located at the interlayer between the Au16Ag3 kernel and the Ag-SR shell. The metastable [Au16Ag43H12(SPhCl2)34]5- can convert to [Au12Ag32(SPhCl2)30]4- spontaneously. Structurally, the Au16Ag3 kernel of [Au16Ag43H12(SPhCl2)34]5- could be regarded as the overlapping of two hollow Au8Ag3 cages via sharing an Ag3 line, which is in contrast to the solely icosahedral Au12 kernel of [Au12Ag32(SPhCl2)30]4-. Besides, the overall construction of Au16Ag43 or Au12Ag32 follows a complementing or overlapping assembly mode, respectively. Overall, the structural anatomy of Au16Ag43H12(SPhCl2)34 sheds some new insight into the structural evolution of metal nanoclusters.

16.
Dalton Trans ; 50(32): 11099-11105, 2021 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-34318845

RESUMO

Hydrogen is a promising substitute for non-renewable fossil fuels. Producing hydrogen fuel by electrolyzing water is an effective strategy to address the growing environmental problems. Platinum (Pt) is still the most active electrocatalyst to catalyze the hydrogen evolution reaction (HER) in alkaline media. Herein, we demonstrate that ultrafine candied haws-shaped PtWNi nanoalloys modified with the Ni species (Nin+) could be formed in the alkaline electroactivation process of PtWNi alloys. Notably, the Ni species (Nin+) promoted the decomposition of water and produced hydrogen intermediates, which were then immediately adsorbed on the surface of Pt and recombined into molecular hydrogen. Moreover, these hydrogen intermediates also enhanced the instability of the HO-H bond, leading to an increase in the total activity.

17.
J Mater Chem B ; 9(32): 6396-6405, 2021 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-34313290

RESUMO

Exploring and developing a new type of nanoplatform with diagnosis and treatment to effectively cure tumors and reduce side effects has become a hot spot for researchers and is of great significance. Herein, a cancer theranostic nanoplatform with dual-imaging, dual-phototherapy and laser-responsiveness to tumor microenvironment was successfully assembled by liposome (Lip) co-loaded with oil-soluble Au4Cu4 nanoclusters (NCs) and water-soluble Au25 NCs via a simple film hydration method and subsequent extraction process. The prepared Au4Cu4/Au25@Lip nanoplatform with core-shell structure and about 50 nm of uniform sphere shape presented highly biocompatible, stability and passive targeting due to the enhanced permeability and retention (EPR) effect. Furthermore, the Lip composed of lecithin and cholesterol has good affinity with the cell membrane, which can realize the effective accumulation of photosensitizers at the tumor site, so that improving phototherapy effect and reducing the damage to normal tissue. The loaded oil-soluble Au4Cu4 NCs were firstly and pleasantly surprised to find possessed not only ideal photodynamic effect, but also preferable catalysis towards endogenous hydrogen peroxide (H2O2) decomposition to produce oxygen (O2) for improving the tumor hypoxic environment besides the excellent photoluminescence ability while the water-soluble Au25 NCs own outstanding photothermogenesis effect and also photoluminescence performance. The in vitro and in vivo experiment results proved that in the Au4Cu4/Au25@Lip nanoplatform, the performances of both NCs were complementary, which presenting considerable photothermal/fluorescence imaging (PTI/FI)-guided synergistic photothermal therapy (PTT)/O2-enhanced photodynamic therapy (PDT) effect for the tumor under the irradiation of near infrared (NIR) laser. This work provides a useful inspiration and paves a new way for the assembly of NCs or namomaterials with different properties into an integrated anti-tumor theranostic nanoplatform.

18.
J Phys Chem Lett ; 12(28): 6654-6660, 2021 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-34255522

RESUMO

Halogens have widely served as handles for regulating the growth of nanoparticles and the control of their physicochemical properties. However, their regulatory mechanism is poorly understood. Nanoclusters are the early morphology of nanoparticles and play an important role in revealing the formation and growth of nanoparticles due to their precise structures. Here, we report that halogens induce the anisotropic growth of Ag40(C6H5COO)13(SR)19(CH3CN) (Ag40-II, where SR = 4-tert-butylbenzylmercaptan) into Ag45(C6H5COO)13(SR)22Cl2 (Ag45), where Ag40-II is converted from Ag40(CH3COO)10(SR)22 (Ag40-I). Experiments and theoretical simulations showed that halogen ions adsorb at both ends of the cluster, forming defect sites. The -SR-Ag- complexes fill the defects and complete the anisotropic transition from Ag40-II to Ag45. Circular dichroism spectra show that the chirality of Ag45 decreases 15-fold compared with that of Ag40-II. This work provides important insights into the effects of halogens on the growth mechanism and property regulation for nanomaterials at the atomic level and the benefits of further applications of halogen-induced nanomaterials.


Assuntos
Halogênios/química , Nanoestruturas/química , Anisotropia , Modelos Moleculares , Conformação Molecular , Prata/química , Estereoisomerismo
19.
J Am Chem Soc ; 143(30): 11317-11324, 2021 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-34293258

RESUMO

The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni2(dppm)2Cl3 dinuclear-cluster-derived strategy to a uniform atomically precise Ni2 site, consisting of two Ni1-N4 moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using operando synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni2 structure under electrochemical CO2 reduction reaction, revealing an oxygen-bridge adsorption on the Ni2-N6 site to form an O-Ni2-N6 structure with enhanced Ni-Ni interaction. Theoretical simulations demonstrate that the key O-Ni2-N6 structure can significantly lower the energy barrier for CO2 activation. As a result, the dinuclear Ni2 catalyst exhibits >94% Faradaic efficiency for efficient carbon monoxide production. This work provides bottom-up target synthesis approaches and evidences the identity of dinuclear sites active toward catalytic reactions.

20.
Nanoscale ; 13(24): 10816-10828, 2021 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-34113940

RESUMO

Cancer is still a major threat to human health at present. Developing new types of integrated nanoplatforms for the accurate diagnosis and effective treatment of cancer is very significant. Herein, an intelligent dual-stage core-shell cancer theranostic nanoplatform (Fe3+@Au1Ag24@PbP) with NIR laser/tumor-microenvironment (TME) co-responsiveness and multi-modal imaging-therapy was successfully prepared, which was composed of the precisely structured oil-soluble Au1Ag24 nanoclusters (NCs) and Fe3+ ions easily assembled within the oil and aqueous phases of the polyethylene glycol (PEG) block grafted polyketal (PK) copolymer (PK-b-PEG, PbP) vesicles, respectively. In this system, we were delighted to find that the prepared Au1Ag24 NCs possess multi-photoresponsive properties, endowing the nanoplatform with photoacoustic (PA)/photothermal (PT) imaging and synergetic photothermal therapy (PTT)/photodynamic therapy (PDT) for cancer under near-infrared (NIR) laser irradiation. On the other hand, Fe3+ ions exhibit multi-TME response and regulation behaviors, including as catalysts for the decomposition of endogenous hydrogen peroxide (H2O2) in the solid tumor to produce O2 and as the oxidizing agent for the consumption of the intracellular GSH to avoid the reduction of the generated 1O2; therefore, the synchronously formed Fe2+ ions from the redox of Fe3+ with GSH could further react with H2O2 to produce hydroxyl radical (˙OH), which induced ferroptosis-based cancer treatment. The PbP shell possesses TME/pH sensitivity for controlled drug release and passive targeting, causing a large increase in Au1Ag24/Fe3+ accumulation within the weakly acidic tumor region and reducing the side effects on normal tissues. Both in vitro and in vivo experiments demonstrate that the Fe3+@Au1Ag24@PbP nanoplatform presented excellent PA/PT imaging-guided synergetic PTT/PDT/ferroptosis effects toward tumor cells and tumors. This integrating multi-responsive and multi-modal theranostic nanoplatform paves a new way for effective cancer therapy.


Assuntos
Nanopartículas , Neoplasias , Fotoquimioterapia , Linhagem Celular Tumoral , Humanos , Peróxido de Hidrogênio , Lasers , Imagem Multimodal , Fototerapia , Medicina de Precisão , Nanomedicina Teranóstica
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