Synthesis and luminescence of a charge-neutral, cyclometalated iridium(III) complex containing N--C--N- and C--N--C-coordinating terdentate ligands

The first examples of iridium(III) complexes containing a terdentate, N--C--N-coordinated 1,3-di(2-pyridyl)benzene derivative, cyclometalated at C2 of the benzene ring, are reported. This mode of binding becomes significant only if competitive cyclometalation at C4/C6 is blocked, and the ligand 1,3-di(2-pyridyl)-4,6-dimethylbenzene (dpyxH) has been prepared to achieve this condition. The charge-neutral complex [Ir(dpyx)(dppy)], 2, (dppyH(2) = 2,6-diphenylpyridine) has been isolated, containing dpyx and dppy bound to the metal through one and two carbon atoms, respectively. A terpyridyl analogue, [Ir(dpyx)(ttpy)](PF(6))(2), 3, (ttpy = 4'-tolylterpyridine) has also been prepared and its X-ray crystal structure determined, confirming the N--C--N binding mode of dpyx. Complex 2 emits strongly in degassed solution at 295 K (lambda(max) = 585 nm, phi = 0.21, tau = 3900 ns, in CH(3)CN). In solution, the excited state can also undergo photodissociation, through cleavage of one of the Ir-C(dppy) bonds.     

Synthesis of optically pure (+)-puraquinonic acid and assignment of absolute configuration to natural (-)-puraquinonic acid. Use of radical cyclization for asymmetric generation of a quaternary center

An asymmetric aldol reaction between aldehyde 31 and imide 32, followed at a later stage by ring-closing metathesis (38 --> 40), are key reactions used to make optically pure allylic alcohol 40. Radical cyclization of the derived Stork bromo acetals gives lactol ethers 43, which were degraded to generate a quaternary center carrying a methoxycarboxyl group (44 --> 47). Compound 47 was converted into (+)-puraquinonic acid; and comparison with a natural sample established that the configuration of the natural compound is 2R (1).     

Synthesis of (+/-)-hamigeran B, (-)-hamigeran B, and (+/-)-1-epi-hamigeran B: use of bulky silyl groups to protect a benzylic carbon-oxygen bond from hydrogenolysis

Enone 42 was converted into diene 56, which was then subjected to hydrogenation. Use of the tert-butyldimethylsiloxy groups enforces facial selectivity and protects the C(5) oxygen from hydrogenolysis. The resulting product (55) is easily converted into hamigeran B (1), a marine natural product with powerful activity against herpes and polio viruses. Optically pure enone 73 was made by use of a Meyers' auxiliary and converted into (-)-hamigeran B with the natural absolute configuration.     

Synthesis of 4,4-difluoroglycosides using ring-closing metathesis

4-Deoxy-4,4-difluoro-glycosides have been synthesised for the first time via a direct sequence involving ring-closing metathesis and indium-mediated difluoroallylation with 1-bromo-1,1-difluoropropene in water. Two protecting group strategies were explored, one to allow protection of the primary C-6 hydroxyl group throughout the sequence, while the second was intended to allow deprotection after RCM and before dihydroxylation. The benzyl ether could be used in the first role, and pivaloyl is effective in the second. Dihydroxylations were highly stereoselective and controlled by the orientation of the glycosidic C-O bond.     

Oxygen sensitivity of red cell membrane transporters revisited

In this paper, we provide an update on O2-dependent membrane transport in red cells. O2-sensitive membrane transport was compared in nucleated (chicken) and enucleated (human) red cells, to investigate effects on organic (glucose transporter [GLUT]) and inorganic (K(+)-Cl- cotransporter [KCC]/Na(+)-K(+)-2Cl- cotransporter [NKCC]) transporters, to study the response of so-called "housekeeping" transporters (Na+/K+ pump and anion exchanger [AE]) and, finally, to compare O2 sensitivity in normal human red cells with those from sickle cell patients. The Na+/K+ pump showed no change in activity between oxygenated and deoxygenated cells in any of the samples. KCC in normal human red cells had the greatest O2 sensitivity, being stimulated some 20-fold on oxygenation. It was more modestly stimulated by O2 in chicken red cells and HbS cells. By contrast, NKCC was stimulated by deoxygenation in all cases. GLUT showed little response to O2 tension, other than a small stimulation in deoxygenated chicken red cells. Finally, AE1 was stimulated by oxygenation in HbA cells, but this stimulation by O2 was absent in HbS cells and pink ghosts prepared from HbA cells. The significance of these findings is discussed.     

Engineered biosynthesis of novel spinosyns bearing altered deoxyhexose substituents

Novel spinosyns have been prepared by biotransformation, using a genetically engineered strain of Saccharopolyspora erythraea, in which the beta-D-forosamine moiety in glycosidic linkage to the hydroxy group at C17 is replaced by alpha-L-mycarose.     

Nanojunction‐Mediated Photocatalytic Enhancement in Heterostructured CdS/ZnO,CdSe/ZnO,and CdTe/ZnO Nanocrystals

A series of highly efficient semiconductor nanocrystal (NC) photocatalysts have been synthesized by growing wurtzite‐ZnO tetrahedrons around pre‐formed CdS, CdSe, and CdTe quantum dots (QDs). The resulting contact between two small but high‐quality crystals creates novel CdX/ZnO heterostructured semiconductor nanocrystals (HSNCs) with extensive type‐II nanojunctions that exhibit more efficient photocatalytic decomposition of aqueous organic molecules under UV irradiation. Catalytic testing and characterization indicate that catalytic activity increases as a result of a combination of both the intrinsic chemistry of the chalcogenide anions and the heterojunction structure. Atomic probe tomography (APT) is employed for the first time to probe the spatial characteristics of the nanojunction between cadmium chalcogenide and ZnO crystalline phases, which reveals various degrees of ion exchange between the two crystals to relax large lattice mismatches. In the most extreme case, total encapsulation of CdTe by ZnO as a result of interfacial alloying is observed, with the expected advantage of facilitating hole transport for enhanced exciton separation during catalysis.     

Crystalographic and structural characterization of heterometallic platinum compounds. Part III: heterotrinuclear compounds

This review article includes over three hundred and sixty heterotrinuclear platinum complexes of the composition Pt₂M (205 examples), PtM₂ (132 examples) and PtMM (24 examples). The heterometals include the non-transition and transition metals. Three metal atoms form a wide variability of frameworks: M₃ triangular, dicapped M₃ triangular, V shaped M₃, M₃ linear, five-, six- and seven- metallocycles and unique structures of which triangular and linear are the most common. This has led to a rich chemistry of platinum not only from variability of metals, but also from their framework and stereochemistry. The shortest Pt-M (non-transition) and Pt-M (transition) bonds are 2.315(1) Å for Pt-Ga and 2.4896(9) Å for Pt-Co. The shortest Pt-Pt bond distance is 2.581(1) Å. Two complexes exist in two isomeric forms and several others contain crystallographically independent molecules. All are typical examples of distortion isomerism. Correlations between structural parameters, heterometal and ligand donor atoms are developed and discussed.