Structures of the NDP-pyranose mutase belonging to glycosyltransferase family 75 reveal residues important for Mn2+ coordination and substrate binding.

Members of glycosyltransferase family 75 (GT75) not only reversibly catalyze the autoglycosylation of a conserved arginine residue with specific NDP-sugars but also exhibit NDP-pyranose mutase activity that reversibly converts specific NDP-pyranose to NDP-furanose. The latter activity provides valuable NDP-furanosyl donors for glycosyltransferases and requires a divalent cation as a cofactor instead of FAD used by UDP-D-galactopyranose mutase. However, details of the mechanism for NDP-pyranose mutase activity are not clear. Here we report the first crystal structures of GT75 family NDP-pyranose mutases. The novel structures of GT75 member MtdL in complex with Mn2+ and GDP, GDP-D-glucopyranose, GDP-L-fucopyranose, GDP-L-fucofuranose, respectively, combined with site-directed mutagenesis studies, reveal key residues involved in Mn2+ coordination, substrate binding, and catalytic reactions. We also provide a possible catalytic mechanism for this unique type of NDP-pyranose mutase. Taken together, our results highlight key elements of an enzyme family important for furanose biosynthesis.

Chiral Amphiphilic Au23 Cluster and Its Specific Recognition to Remote Di-amines.

The atomic precision of metal nanoclusters and variability of surface ligands pave the way for its rational design and functionalization, whereas the property strengthening in multiple ways has been long challenging. Herein, improved amphiphilicity, chirality, thermostability, and strong CPL (circularly polarized luminescence) properties have been accomplished by facile ligand exchange of [Au23(CHT)16]- with HCapt (HCHT and HCapt denote cyclohexanethiol and captopril). In addition, the obtained chiral [Au23(SR)16]- (short for [Au23(CHT)16-x(Capt)x]-) clusters show specific binding affinity to remote-diamines (such as arginine and single/double strand DNA), originating from the hydrogen bonding and Van der Walls interaction among the surface Capt ligands and the di-amine groups.

Bimetallic Ag125Cu8 Nanocluster, Structure Determination, and Nonlinear Optical Properties.

The atomic precision of the subnanometer nanoclusters has provided sound proof on the structural correlation of metal complexes and larger-sized metal nanoparticles. Herein, we report the synthesis, crystallography, structural characterization, electrochemistry, and optical properties of a 133-atom intermetallic nanocluster protected by 57 thiolates (3-methylbenzenethiol, abbreviated as m-MBTH) and 3 chlorides, with the formula of Ag125Cu8(m-MBT)57Cl3. This is the largest Ag-Cu bimetallic cluster ever reported. Crystallographic analysis revealed that the nanocluster has a three-layer concentric core-shell structure, Ag7@Ag47@Ag71Cu8S57Cl3, and the Ag54 metal kernel adopts a D5h symmetry. The nuclei number is between that of the previously reported large silver cluster [Ag136(SR)64Cl3Ag0.45]- and the large silver-rich cluster Au130-xAgx(SR)55 (x = 98). All these three clusters bear a similar metallic core structure, while the main structural difference lies in the shell motif structures. Electron counting revealed an open electron shell with 73 delocalized electrons, which was verified by the electron paramagnetic resonance analysis. The DPV electrochemical measurement indicates a multielectron state quantization double-layer charging shape and single-electron sequential charging and discharging characteristic of the AgCu alloy cluster. In addition, the open-hole Z-scan test reveals the nonlinear optical absorption (2-3 optical absorption in the NIR-II/III region) of Ag125Cu8 nanoclusters.

Symmetry Breaking Enhancing the Activity of Electrocatalytic CO2 Reduction on an Icosahedron-Kernel Cluster by Cu Atoms Regulation.

Recently, CO2 hydrogenation had a new breakthrough resulting from the design of catalysts to effectively activate linear CO2 with symmetry-breaking sites. However, understanding the relationship between symmetry-breaking sites and catalytic activity at the atomic level is still a great challenge. In this study, a set of gold-copper alloy Au13 Cux (x=0-4) nanoclusters were used as research objects to show the symmetry-controlled breaking structure on the surface of nanoclusters with the help of manipulability of the Cu atoms. Among them, Au13 Cu3 nanocluster displays the highest degree of symmetry-breaking on its crystal structure compared with the other nanoclusters in the family. Where the three copper atoms occupying the surface of the icosahedral kernel unevenly with one copper atom is coordinately unsaturated (CuS2 motif relative to CuS3 motif). As expected, Au13 Cu3 has an excellent hydrogenation activity of CO2 , in which the current density is as high as 70 mA cm-2 (-0.97 V) and the maximum FECO reaches 99 % at -0.58 V. Through the combination of crystal structures and theoretical calculations, the excellent catalytic activity of Au13 Cu3 is revealed to be indeed closely related to its asymmetric structure.

Cu(I)-Glutathione Assembly Supported on ZIF-8 as Robust and Efficient Catalyst for Mild CO2 Conversions.

The Cu-glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF-8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single-atom Cu(I) catalyst. Synergy between Cu(I) and ZIF-8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high-value-added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency.

Cd Atom Goes into the Interior of Cluster Induced by Directional Consecutive Assembly of Tetrahedral Units on an Icosahedron Kernel.

"Core sliding" in metal nanoclusters drives the reconstruction of external structural units and provides an ideal platform for mapping their precise transformation mechanism and evolution pathway. However, observing the movement behavior of metal atoms in experiments is still challenging because of the uncertain stability of intermediates. In this work, a series of Au-Cd alloy nanoclusters with continuously assembled kernels (one icosahedral building block assembled with 0 to 3 tetrahedral units) were constructed. As the assembly continued, it eventually led to the Cd atom doping into the inner positions of the clusters. Importantly, the Cd doped into the interior of the cluster exhibits a different behavior than the surface or external Cd atoms (dispersion doping vs localized occupy), which provides experimental evidence of the sliding behavior in the nanocluster kernel. Furthermore, density functional theory (DFT) calculations reveal that this sliding behavior in the inner sites of nanoclusters is an energetically favorable process. In addition, these Au-Cd nanoclusters exhibit tunable optical properties with different assembly patterns in their kernels.

DFT Insights into the Variety in the Coordination Modes of the Equatorial Halides in [Au13 Ag12 (PR3 )10 X8 ]+ (X=Cl/Br) Clusters.

The bonding character within metal nanoclusters represents an intriguing topic, shedding light on the inherent driving force for the packing preference in nanomaterials. Herein, density functional theory (DFT) calculations were conducted to investigate the correlation of the series of isomeric [Au13 Ag12 (PR3 )10 X8 ]+ (X=Cl/Br) clusters, which are mainly differentiated by the coordination mode of the equatorial halides (µ2 -, µ3 - and µ4 -) in the rod-like, bi-icosahedral framework. The theoretical simulation corroborates the variety in the configuration of the Au13 Ag12 clusters and elucidates the fast isomerization kinetics among the different configurations. The easy tautomerization and the variety in chloride binding modes correspond to a fluxionality character of the equatorial halides and are verified by the potential energy curve analysis. The structural flexibility of the central Au3 Ag10 block is the main driving force, while the relatively stronger Ag-X bonding interaction (compared to that of Au-X), and a sufficient number of halides are also requisite for the associating Ag-X tautomerizations.

Motif-to-Core Nucleation in a Decahedral Evolution Pattern.

The atomic precision of ultrasmall metal nanoclusters has opened the door to elucidating the structural evolution principles of metal nanomaterials at the molecular level. Here, we report a novel set of super-atomic Ag clusters, including [Ag19(TBBT)16(DPPP)4]+ (Ag19), [Ag22(DMAT)8(DPPM)4Cl8]2+ (Ag22), Ag26(SPh3,5-CF3)15(DPPF)4Cl5 (Ag26), and [Ag30(DMAT)12(DPPP)4Cl8]2+ (Ag30). The core structures of these clusters correspond to one decahedral Ag7, perpendicular bi-decahedrons, three-dimensional penta-decahedrons, and hexa-decahedrons, respectively. The Ag atoms in AgS2 blocks show a strong correlation with the decahedral cores: the five equatorial Ag atoms in the decahedral Ag7 core of Ag19 all adopt the AgS2 coordination, while the Ag atoms in AgS2 blocks of Ag22, Ag26, and Ag30 unexceptionally constitute additional decahedral structures with the core Ag atoms. Specifically, two and four core Ag atoms of Ag26 and Ag30 clusters occupy positions that highly resemble that of Ag (in AgS2 motifs) of Ag22. The strong structural correlation demonstrates the motif-to-core evolution of the surface Ag (on AgS2) to build extra-decahedral blocks. Density functional theory calculations indicate that the 2e, 4e, 6e, and 8e clusters (from Ag19 to Ag30) adopt 1S2, 1S21P2, 1S21P4, and 1S21P6 electron configurations, all of which feature excellent super-atomic characters.

Activity of Different AunSn+1 Staples in the Ligand Exchange of Au23(SR)16- with a Single Foreign Thiolate Ligand.

Ligand exchange has been widely used to synthesize novel thiolated gold nanoclusters and to regulate their specific properties. Herein, density functional theory (DFT) calculations were conducted to investigate the kinetic profiles of the ligand exchange of the [Au23(SCy)16]- nanocluster with an aromatic thiolate (2-napthalenethiol). The three types of staple motifs (i.e., trimetallic Au3S4, monometallic AuS2, and the bridging thiolates) of the Au23 cluster precursor could be categorized into eight groups of S sites with different chemical environments. The ligand exchange of all of them occurs favorably via the SN1-like pathway, with one site starting with the Au-S dissociation and seven other sites starting with the H-transfer steps. By contrast, the SN2-like pathway (i.e., the synergistic SCy-to-SAr exchange prior to the H-transfer step) is unlikely in the target systems. Meanwhile, the Au-S bond on the capping Au atom of the bicapped icosahedral Au15 core is the most active one, while the S sites on Au3S4 (except for the one remote from the metallic core) are all competitive exchanging sites. The ligand exchange activity of the bridging thiolate and the remote S site on Au3S4 is significantly less reactive. The calculation results correlate with the multiple ligand exchange within only a few minutes and the preferential etching of the AuS2 staple with the foreign ligands reported in earlier experiments. The relative activity of different staples might be helpful in elucidating the inherent principles in the ligand exchange-induced size-evolution of metal nanoclusters.

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au6(dppp)4]2+ to [Au8(dppp)4Cl2]2.

Oxidation-induced conversion of gold nanoclusters is an important strategy for preparing novel atomically precise clusters and elucidating the kinetic correlations of different clusters. Herein, the oxidation-induced growth from [Au6(dppp)4]2+ to [Au8(dppp)4Cl2]2+ (reported by Konishi and co-workers) has been studied by density functional theory calculations. A successive oxidation → Cl- coordination → oxidation → Cl- coordination sequence occurs first to activate the Au6 structure, resulting in the high Au(core)-Au(corner) bond cleavage activity and the subsequent formation of [Au2(dppp)2Cl]+ and [Au4(dppp)2Cl]+ fragments. Then, the dimerization of two Au4 fragments and the rearrangement of the diphosphine coordination occur to generate the thermodynamically stable [Au8(dppp)4Cl2]2+ products. The proposed mechanism agrees with the experimental outcome for the fast reaction rate and the residual of the Au2 components. Specifically, a multivariate linear regression analysis indicates the strong correlation of the oxidation potential of Au6, Au8, Au23, and Au25 clusters with the HOMO energy, the number of Au atoms, and cluster charge state. The main conclusions [e.g., oxidation-induced Au(corner)-Au(core) bond activation, easy 1,2-P transfer steps, etc.] of this study might be widely applicable in improving our understanding of the mechanism of other cluster-conversion reactions.