Octyl-type monolithic columns of 530 microm i.d. for capillary liquid chromatography

A novel monolithic capillary column (530 microm i.d.) was prepared for capillary liquid chromatography (CLC) by in situ copolymerization of octyl methacrylate (MAOE) and ethylene dimethacrylate (EDMA) in the presence of a porogen solvent containing 1-propanol, 1,4-butanediol, and water with azobisisobutyronitrile as the initiator. The influences of the contents of the porogen solvent, EDMA and the various concentration ratios of 1-propanol to 1,4-butanediol in the polymerization mixture on the morphology, porosity, globule size, stability and column efficiency were investigated. The morphology and pore size distribution of monolithic capillary columns were characterized by SEM and mercury intrusion porosimetry, respectively. Chromatographic evaluations of the columns were performed under CLC mode. The results showed that good permeability and stability can be obtained under optimal experimental conditions. The separation results of some acid, neutral and basic analytes demonstrated the hydrophobicity and low affinity to basic analytes of the new column. Three metal ions, i.e. Mg(II), Zn(II) and Cd(II) were also separated under ion-pair mode on the new monolithic capillary column and the results were acceptable.     

Green photoluminescence from platinum(II) complexes bearing silylacetylide ligands

The synthesis, structural characterization, photoluminescence properties, and density functional theory analysis of three Pt(II) diimine complexes, Pt(dbbpy)(C triple bond CR)2 [dbbpy = 4,4'-di(tert-butyl-2,2'-bipyridine; R = -SiMe3, -CC-SiMe3, or -t-Bu], are presented. The Pt(dbbpy)(C triple bond C-tBu)2 complex serves as a carbon-based ligand structure for which the photophysical properties of the two silicon-bearing complexes are compared in dichloromethane. Pt(dbbpy)(C triple bond C-SiMe3)2 and Pt(dbbpy)(C triple bond C-C triple bond C-SiMe3)2 display visible absorptions with strong green emission (lambda(emmax) = 526 and 524 nm, respectively) while Pt(dbbpy)(C triple bond C-t-Bu)2 displays efficient, long-lived yellow emission (lambda(emmax) = 557 nm). Direct side by side comparisons of Pt(dbbpy)(C triple bond C-SiMe3)2 and Pt(dbbpy)(C triple bond C-t-Bu)2 suggest that the difference in excited state energy results from the relative sigma-donor strength of the acetylide ligands.     

Star-shaped and linear nanosized molecules functionalized with hexa-peri-hexabenzocoronene: synthesis and optical properties

[structure: see text] A synthetic strategy promising the establishment of a new star-shaped and linear polycyclic aromatic hydrocarbons (PAHs) family with distinct molecular topologies has been developed. The Sonogashira reaction between the iodide derivatives 2a-e and phenylacetylene catalyzed with Pd(0) affords 3a-e in high yields. The Diels-Alder and decarbonylation reactions between 3a-e and tetraphenylcyclophentadiene following the oxidation by FeCl(3) produce the star-shaped and linear PAHs 5a-e containing a five-membered ring. The structural analysis and the optical properties of all new compounds are performed by a combination of MALDI-TOF mass spectrometry, UV-vis, and fluorescence spectrometry. The electronic and photophysical properties are studied by orthogonal comparisons of the absorption and fluorescence spectra in THF solutions, which not only give insight into the interactions among aromatic submoieties in each molecule and the effects of meta-conjugation and para-conjugation on electronic delocalization, but also indicate effective conjugation length variations from oligophenylacetylenes 3a-e to oligophenylene dendrimers 4a-e and PAHs 5a-e. The star-shaped 5c exhibits the highest aggregation in excited states compared with the other four hexa-peri-hexabenzocoronene (HBC) derivatives.     

Oxidative cyclorelease from soluble polymeric supports

[reaction: see text] Single electron oxidation is shown to be a viable method for effecting concomitant cyclization and cleavage (cyclorelease) of a series of polymer bound homobenzylic ethers. Soluble oligonorbornene polymers are stable toward redox chemistry and are isolable through precipitation with methanol, making them excellent supports for this process. These oxidative conditions are also shown to cleave secondary and tertiary alcohols and ethers in a new traceless approach to polymer-supported aldehyde and ketone synthesis.     

Core/shell quantum-dot-photosensitized nano-TiO2 films: fabrication and application to the damage of cells and DNA

Through the use of monodisperse core/shell quantum dots (QDs) as photosensitizers for the first time, a novel strategy for the fabrication of QD-photosensitized nano-TiO2 films was demonstrated. Core/shell QDs were self-assembled on nano-TiO2 films through carboxyls as anchoring groups to metal oxides. Atomic force microscopy and some other experiments showed the fabrication strategy is successful. Reactive oxygen species detection experiments indicated that such films have photosensitization ability. The results of bactericidal and DNA damage experiments demonstrate that such films have excellent photoactivity.     

Theoretical studies of dissociative phosphoryl transfer in interconversion of phosphoenolpyruvate to phosphonopyruvate: solvent effects, thio effects, and implications for enzymatic reactions

The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed.     

Reduction and reconstruction of Co3O4 nanocubes upon carbon deposition

We describe a synthetic investigation on the formation of carbon nanofibers using a preshaped free-standing metal-oxide catalyst (single-crystal cobalt oxide (Co(3)O(4)) nanocubes). In reacting with acetylene (C(2)H(2)) vapor, Co(3)O(4) nanocubes are reduced and reconstructed into metallic cobalt. The resultant metal catalyst with a 2-fold symmetry leads to a bilateral base growth for carbon nanofibers. Our findings indicate that an understanding of catalyst-assisted chemical vapor deposition (CVD) mechanisms can be acquired, when the shape, size, and crystal orientation of pristine metal catalysts are made known to the CVD process. By tracing their evolutional changes in structure and composition, the shape-designed model catalysts may offer new opportunities for mechanistic investigations on the chemical reactivity of nanoparticles, general catalyst-assisted material synthesis, and metal intercalation chemistry.     

CoMFA, CoMSIA, and molecular hologram QSAR studies of novel neuronal nAChRs ligands-open ring analogues of 3-pyridyl ether

3-Pyridyl ethers are excellent nAChRs ligands, which show high subtype selectivity and binding affinity to alpha4beta2 nAChR. Although the quantitative structure-activity relationship (QSAR) of nAChRs ligands has been widely investigated using various classes of compounds, the open ring analogues of 3-pyridyl ethers have been less involved in these studies due to the greater flexibility of this kind of molecule. In this study, two three-dimensional QSAR techniques and one two-dimensional QSAR technique were used to correlate the molecular structure with the biological activity of 64 analogues of 3-pyridyl ethers. Three different QSAR models were established. Their performances in the QSAR studies of open ring analogues of 3-pyridyl ethers were evaluated by the statistical values in the corresponding models. All models exhibited satisfactory predictive power. Of these models, the HQSAR behaved optimally in terms of the statistical values with q2=0.845, r2=0.897. Finally, graphic interpretation of three different models provided coincident information about the interaction of the ligand-receptor complex and supplied useful guidelines for the synthesis of novel, potent ligands.     

A New Hydroxo‐bridged Chromium(III) Dimer [Cr(saltn)OH]2·4H2O: Synthesis,Crystal Structure and Magnetic Properties

A new hydroxo‐bridged dimeric Cr(III) complex [Cr(saltn)OH]₂·4H₂O [H₂saltn=N,N′‐bis(salicylidene)trimethylenediamine] has been synthesized and its structural and magnetic properties have been investigated. The complex crystallizes in the triclinic space group P‐1 with one dimeric formula unit in a cell of dimensions a=0.95828(19) nm, b=0.95926(19) nm, c=1.0437(2) nm, α=86.77(3)°, β=82.48(3)°, and γ=64.93(3)°. The geometry around each chromium(III) center is six‐coordinate, distorted‐octahedral. The bridging Cr₂O₂ unit is strictly planar, as required by the crystallographic symmetry. The Cr? O? Cr′ bridging angle is 99.94(16)°, and the distance between Cr…Cr′ is 0.3019 nm. The magnetic susceptibility of the complex has been examined in the range of 2‐300 K. By using the spin‐spin coupled model for an S₁=S₂=3/2 dimeric system , the magnetic data were fitted to give the parameters of g=2.01(1), J=‐0.85(2) cm^‐1, and zJ' =0.18(3)cm^‐1, indicating the presence of a weak antiferromagnetic spin‐exchange interaction between the Cr(III) ions in the binuclear complex.     

A new chain‐like cadmium(II) coordination polymer containing chains of water mol­ecules

The title cadmium(II) polymer, catena‐poly[[[bis­(4‐amino­pyridine‐κN)­aqua­cadmium(II)]‐μ‐1,4‐phenyl­enediacetato‐κ⁴O,O′:O′′,O′′′] dihydrate], {[Cd(C₁₀H₈O₄)(C₅H₆N₂)₂(H₂O)]·2H₂O}_n, comprises one‐dimensional wave‐like chains, in which the Cd atom is coordinated by 1,4‐phenyl­enediacetate and 4‐amino­pyridine molecules. The 1,4‐phenylenediacetate ligands lie about inversion centres. Extensive hydrogen‐bonding inter­actions between the chains lead to a three‐dimensional structure. Free water mol­ecules form chains in the structure.