Syntheses, structures, and photoluminescence properties of metal(II) halide complexes with pyridine-containing flexible tripodal ligands

Seven coordination compounds, [Zn(L3)Cl2] . MeOH . H2O (1), [Mn(L3)2Cl2] . 0.5EtOH . 0.5H2O (2), [Cu3(L2)2Cl6] . 2DMF (3), [Cu3(L2)2Br6] . 4MeOH (4), [Hg2(L4)Cl4] (5), [Hg2(L4)Br4] (6), and [Hg3(L4)2I6] . H2O (7), were synthesized by the reactions of ligands 1,3,5-tris(3-pyridylmethoxyl)benzene (L3), 1,3,5-tris(2-pyridylmethoxyl)benzene (L2), and 1,3,5-tris(4-pyridylmethoxyl)benzene (L4) with the corresponding metal halides. All the structures were established by single-crystal X-ray diffraction analysis. In complexes 1 and 2, L3 acts as a bidentate ligand using two of three pyridyl arms to link two metal atoms to result in two different 1D chain structures. In complexes 3 and 4, each L2 serves as tridentate ligand and connects three Cu(II) atoms to form a 2D network structure. Complexes 5 and 6 have the same framework structure, and L4 acts as a three-connecting ligand to connect Hg(II) atoms to generate a 3D 4-fold interpenetrated framework, while the structure of complex 7 is an infinite 1D chain. The results indicate that the flexible ligands can adopt different conformations and thus can form complexes with varied structures. In addition, the coordination geometry of the metal atom and the species of the halide were found to have great impact on the structure of the complexes. The photoluminescence properties of the complexes were investigated, and the Zn(II), Mn(II) and Hg(II) complexes showed blue emissions in solid state at room temperature.     

Synthesis and Crystal Structure of Blue Luminescent Cadmium(II) Coordination Networks with 4,4′-Bis(imidazol-1-ylmethyl)biphenyl from Different Solvent Systems

Two supramolecular complexes, [Cd(bimb)²Cl²] (1) and [Cd(bimb)(DMF)Cl²]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl²·2.5H²O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks.     

Total Synthesis of Proposed Structure of Yuremamine and All Diastereomers Using [3+2]‐Cycloaddition of Platinum‐Containing Azomethine Ylide

Total synthesis of the proposed structure of yuremamine has been achieved for the first time based on the intermolecular [3+2]‐cycloaddition reaction of the platinum‐containing azomethine ylide. All the possible diastereomers of yuremamine were also synthesized via the common intermediate. Through these syntheses, it was confirmed that the proposed structure of yuremamine and the diastereomers differ from the natural product.     

Control of hole opening in single-wall carbon nanotubes and single-wall carbon nanohorns using oxygen

Due to the simplicity of the process, holes in the graphene walls of single-wall carbon nanotubes (SWNTs) and single-wall carbon nanohorns (SWNHs) have often been opened using O2 gas at high temperatures, even though this contaminates the nanotubes with carbonaceous dust (C-dust). To open holes with less C-dust contamination, we found that a slow temperature increase of 1 degrees C/min or less, in air, was effective. We also found that SWNHs having little C-dust could store a large quantity of materials inside the tubes. We infer that the local temperature increase due to the exothermic reaction of combustion may have been suppressed in the slow combustion process, which was effective in reducing the C-dust.     

Algorithm for in vitro Sun Protection Factor based on transmission spectrum measurement with concomitant evaluation of photostability

In the in vitro evaluation of Sun Protection Factor (SPF), the photostability of the ultraviolet (UV) filters can have a major impact, especially for high-SPF formulations, but is generally not taken into consideration. In this study, we present a UV transmission spectrum measurement system utilizing a high-sensitivity UV photomultiplier tube with concomitant evaluation of photostability. We have developed an algorithm to estimate SPF in vitro by converting the amount of UV light transmission through the sunscreen layer into cumulative relative erythema effectiveness to obtain one minimal erythema dose. Thus, the algorithm uses the same endpoint as in vivo SPF methods, but with a photomultiplier tube as the detector instead of skin. The values obtained showed an excellent correlation with in vivo SPF values, even for high-SPF sunscreens exceeding SPF 50. This method should be suitable as an in vitro SPF testing method for regulatory purposes.     

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)] is reported. Grinding of the complex induced a photoluminescent color change, which was restored by exposure to a solvent. This cycle was repeated 20 times with no color degradation in the emissions. Their optical properties, X-ray crystallographic analysis, IR, and XRD measurements strongly suggested that the change in the molecular arrangement is responsible for this mechanochromic property. Intermolecular aurophilic bondings presumably play a key role in the altered emission.     

Application of electrospray ionization tandem mass spectrometry for the rapid and sensitive determination of cobalt in urine

Recently, cobalt (Co) is reported to be taken as a supplement by athletes for improving anaerobic performance. For the diagnosis of abuse, the limit of detection (LOD) of Co in the analysis should be lower than the concentrations of Co in plasma and urine of normal persons. A simple, rapid and sensitive method has been developed for the determination of Co in urine. Co was complexed with diethyldithiocarbamate (DDC) and extracted with isoamyl alcohol in the presence of citric acid. The detection of Co was achieved by injecting a 1-μL aliquot of isoamyl alcohol containing Co-DDC complex directly into an electrospray ionization tandem mass spectrometric (ESI-MS-MS) instrument without chromatographic separation. The quantification was performed using selected reaction monitoring at m/z 291 of the product ion Co(C₄H₁₀NCS)₂⁺ which was produced by collision-induced dissociation from the precursor ion Co(DDC)₂⁺ at m/z 355. ESI-MS-MS data were obtained in less than 10 min with an LOD of 0.05 μg L⁻¹ and a linear calibration range of 0.1-100 μg L⁻¹ using 10 μL of urine. The procedure was validated with certified reference materials (SRM 2670a and SRM 1643e). This method is suitable for the analysis of Co in the laboratories already equipped with an ESI-MS-MS instrument.     

Phospholipases Induce Melanogenesis in Organ-Cultured Skin

Guinea pig skin becomes more pigmented following exposure to UV rays. This melanization was accompanied by enhanced intensity of tyrosinase-staining and increased number of tyrosinase-positive melanocytes (MEL^ty+), with resultant enhancement of melanin synthesis. To clarify the regulatory mechanism for melanization following UV irradiation, organ-cultured guinea pig skins have been used to examine their melanogenic responses to exogenous stimulation. This organ culture system responded well to UV irradiation, by increasing melanogenic activity. Also, in this system, phospholipases (PL), arachidonic acid, interleukin-1α and melanocytestimulating hormone, but not endothelin-1 or phosphatidylinositol-specific PLC (PI-PLC), stimulated melanogenesis to various extents as indicated by the number of MEL^ty+ and morphological changes. Among them, the PLA₂ and PLD were found to have a potent stimulatory property for melanocytes. They might affect melanocytes directly or indirectly through an effect on keratinocytes. These results suggest that PLA₂ and PLD play a key role in epidermal hyperpigmentation after UV irradiation or inflammation.     

Assembly of Carbohydrates on a Nickel(II) Center by Utilizing N-Glycosidic Bond Formation with Tris(2-aminoethyl)amine (tren). Syntheses and Characterization of [Ni{N-(aldosyl)-tren}(H(2)O)](2+), [Ni{N,N'-bis(aldosyl)-tren}](2+) and [Ni{N,N',N"-tris(aldosyl)-tren}](2+)

Reactions of [Ni(tren)(H(2)O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO(4) (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO(4) (2c); aldosyl = L-rhamnosyl, X(2) = SO(4) (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [Ni(II)N(4)O(2)] complex with the tren acting as a tetradentate ligand (1c.2H(2)O: orthorhombic, Pbca, a = 15.988(2) ?, b = 18.826(4) ?, c = 10.359(4) ?, V = 3118 ?(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine (2a.CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) ?, b = 20.095(4) ?, c = 8.361(1) ?, V = 2689 ?(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) ?, b = 21.823(8) ?, c = 9.746(2) ?, V = 3176 ?(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) ?, b = 21.694(5) ?, c = 9.786(2) ?, V = 3091 ?(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H(2)O)(2)]Cl(2) (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N"-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C(3) symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and (13)C NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO(4).6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N"-(L-rhamnosyl)(3)-tren)(SO(4))] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8.3CH(3)OH.H(2)O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) ?, b = 16.670(7) ?, c = 15.38(1) ?, V = 4111 ?(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C(3) symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr(2).     

A chiral chelating diene as a new type of chiral ligand for transition metal catalysts: its preparation and use for the rhodium-catalyzed asymmetric 1,4-addition

As a new type of chiral ligand, a C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene (1) was prepared and used for the rhodium-catalyzed asymmetric addition of organoboron and -tin reagents to alpha,beta-unsaturated ketones, which gave high yields of the 1,4-addition products with up to 99% enantioselectivity.