Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Structural Principles of Polyhedral Allotropes of Phosphorus

We derive the structural principles of polyhedral allotropes of phosphorus, introducing three distinct families of black phosphorus nanostructures. The predicted tetrahedral, octahedral, and icosahedral phosphorus cages can also be considered as phosphorus fullerenes. Phosphorus cages up to P₈₈₈ are systematically investigated by quantum chemical methods, and their thermodynamic stabilities are compared with the experimentally known allotropic forms of phosphorus. The tetrahedral cages are thermodynamically favored over the octahedral and icosahedral structures, although large octahedral structures become nearly as stable as the tetrahedral ones. The stability trends of the studied polyhedral families can be rationalized on the basis of their structural characteristics. The phosphorus polyhedra can be further stabilized by fitting smaller structures inside larger ones, resulting in multilayered, bulk‐like cages. The synthesis of the predicted black phosphorus nanostructures is suggested to be viable from the thermodynamic point of view, and several approaches for their experimental preparation can be envisaged.     

Supramolecular luminescent gold(I)-copper(I) complexes: self-assembly of the Au(x)Cu(y) clusters inside the [Au3(diphosphine)3]3+ triangles

The reactions between diphosphino-alkynyl gold complexes (PhC2Au)PPh2(C6H4)(n)PPh2(AuC2Ph) (n = 1, 2, 3) with Cu(+) lead to formation of the heterometallic aggregates, the composition of which may be described by a general formula [{Au(x)Cu(y)(C2Ph)2x}Au3{PPh2(C6H4)(n)PPh2}3](3+(y-x)) (n = 1, 2, 3; x = (n + 1)(n + 2)/2; y = n(n + 1)). These compounds display very similar structural patterns and consist of the [Au(x)Cu(y)(C2Ph)2x](y-x) alkynyl clusters "wrapped" in the [Au3(diphosphine)3](3+) triangles. The complex for n = 1 was characterized crystallographically and spectrally, the larger ones (n = 2, 3) were investigated in detail by NMR spectroscopy. Their luminescence behavior has been studied, and a remarkably efficient emission with a maximum quantum yield of 0.92 (n = 1) has been detected. Photophysical experiments demonstrate that an increase of the size of the aggregates leads to a decrease in photostability and photoefficiency. Computational studies have been performed to provide additional insight into the structural and electronic properties of these supramolecular complexes. The theoretical results obtained are in good agreement with the experimental data, supporting the proposed structural motif. These studies also suggest that the observed efficient long-wavelength luminescence originates from metal-centered transitions within the heterometallic Au-Cu core.     

Characterization of the alnumycin gene cluster reveals unusual gene products for pyran ring formation and dioxan biosynthesis

Alnumycin is closely related to the benzoisochromanequinone (BIQ) polyketides such as actinorhodin. Exceptional structural features include differences in aglycone tailoring that result in the unique alnumycin chromophore and the existence of an unusual 4-hydroxymethyl-5-hydroxy-1,3-dioxan moiety. Cloning and sequencing of the alnumycin gene cluster from Streptomyces sp. CM020 revealed expected biosynthesis genes for polyketide assembly, but several genes encoding subsequent tailoring enzymes were highly atypical. Heterologous expression studies confirmed that all of the genes required for alnumycin biosynthesis resided within the sequenced clone. Inactivation of genes aln4 and aln5 showed that the mechanism of pyran ring formation differs from actinorhodin and granaticin pathways. Further inactivation studies identified two genes, alnA and alnB, involved in the synthesis and attachment of the dioxan moiety, and resulted in the production of the polyketide prealnumycin.     

On Borel equivalence relations in generalized Baire space

We construct two Borel equivalence relations on the generalized Baire space κ ^κ , κ ^<κ ?=?κ >?ω, with the property that neither of them is Borel reducible to the other. A small modification of the construction shows that the straightforward generalization of the Glimm-Effros dichotomy fails.     

Promoter effect of BaO on CO oxidation on PdO surfaces

The effect of bulk BaO promoter on CO oxidation activity of palladium oxide phase was studied by density functional calculations. A series of BaO(100) supported Pd(x)O(y) thin layer models were constructed, and energy profiles for CO oxidation on the films were calculated and compared with corresponding profiles for the most stable PdO bulk surfaces PdO(100) and PdO(101). The most stable of the thin films typically exhibit the same PdO(100) and PdO(101) surface planes; the PdO(100) dominates already with double layer thickness. The supporting promoter improves the CO oxidation activity of the Pd(x)O(y) phase via a direct electronic effect and introduced structural strain and corrugation. Changes in CO adsorption strength are reflected in oxidation energy barriers, and the promoting effect of even 0.3 eV can be seen locally. Easier oxygen vacancy formation may partially facilitate the reaction.     

Spectral reflectance estimation for electronic endoscope

A method of spectral reflectance estimation for electronic endoscopes is described. A new approach is proposed for the overfitting problem. We use a small training set. Initially, cross-validation is used to select model parameters. Then, for additional validation of the method a color image acquired under the same illumination as the training data is used. This additional color image gives a clear solution for both the estimation of spectra and the estimation of color reproduced from these spectra. Experiments confirm that the method predicts spectral reflectance and colors well. Accurate reproduction of endoscope images in different viewing conditions and under another light source was implemented using this approach.