Optical second-harmonic generation from a monolayer of centrosymmetric molecules adsorbed on silver

An increase in the optical second-harmonic signal arising from an electrochemically treated silver surface upon adsorption of a monolayer of the centrosymmetric molecule pyrazine is reported and an effective second-order non-linear polariz-ability for the adsorbed species deduced. These investigations illustrate the potential of second-harmonic generation in the elucidation of interfaces.     

STABILITY OF POLY（N,N＇-METHYLENEBISACRYLAMIDE-co-4-VINYLPYRIDINE） MICROGEL DISPERSION AND ADJUSTMENT OF THE HYDROPHOBICITY IN THE MICROGELS

In the UV-Vis spectra of pure light-scattering systems, there is an exponential relationship between absorbance and wavelength （A = Kλ^-n）. Here, the exponent n is named as flocculation-coagulation parameter. In the present paper, the effects of different additives on the stability of poly（N,N＇-methylenebisacrylamide-co-4-vinylpyridine） （poly（Bis-co-4-VP）） microgel dispersion were studied in detail via this parameter. The results showed that the stability of the dispersion mainly comes from the ionization of pyridine groups, making the microgel positively charged on its surface. This was confirmed by the measurement of Zeta potential and the result of conductometric titration. The result of fluorescence analysis indicated that the hydrophobicity in the microgels is enhanced with the increase in total 4-VP unit content.     

Characterization of highly sulfated cyclodextrins

A class of highly sulfated cyclodextrins (HS-CDs) was developed for enantiomeric separation of chiral compounds by capillary electrophoresis (CE). The HS-CDs were produced by a facile single-step direct sulfation of cyclodextrin using sulfur trioxide-trimethylamine complex in dimethylformamide. Characterization of the HS-CDs by electrospray ionization mass spectrometry and by CE using a well-established indirect detection method indicated the species have very narrow heterogeneity in terms of degree of sulfation. Elemental analysis of the HS-alpha-, beta- and gamma-CDs showed that the average sulfate contents were 11, 12, and 13 per CD molecule, respectively. The 13C NMR of HS-CDs is consistent with the structural assignment of nearly complete sulfation at C-6 primary hydroxyl groups and partial sulfation at the C-2 secondary hydroxyls (>70%), while the C-3 hydroxyls remain unsubstituted. Enantiomeric separation by CE using the HS-CDs as chiral selectors showed that HS-alpha-, beta- and gamma-CDs complement each other by exhibiting different chiral selectivities, resulting in resolution of many chiral neutral, acidic and basic compounds of greatly varying structural features. The part of HS-CD that interacts with the guest molecule during complexation and, therefore, the receiving end of the cyclodextrin hydrophobic bucket was surrounded with largely regiospecifically substituted C-2 sulfates and intact C-3 hydroxyls, both at the equatorial positions. Such global regiospecific structural arrangement in HS-CDs provides differential diasteroisomeric complexation is proposed to be the principal contributing factor in the resolving racemates.     

Synthesis, crystal structure and magnetic property of the novel dinuclear nickel(II) complex with 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole

A novel dinuclear nickel(II) complex, [Ni₂(MOBPT)₂Cl₂(H₂O)₂]Cl₂ · 7H₂O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction methods. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planer in which each Ni^II ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex.     

Optical properties of ZnO and ZnO:In nanorods assembled by sol-gel method

Self-assembled zinc oxide (ZnO) and indium-doping zinc oxide (ZnO:In) nanorod thin films were synthesized on quartz substrates without catalyst in aqueous solution by sol-gel method. The samples were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM), Raman-scattering spectroscopy, room-temperature photoluminescence (PL) spectra, and temperature-dependent PL spectra measurements. XRD and Raman spectra illustrated that there were no single In2O3 phase in ZnO lattice after indium doping. The PL spectra of ZnO showed a strong UV emission band located at 394 nm and a very weak visible emission associated with deep-level defects. Indium incorporation induced the shift of optical band gap, quenching of the near-band-edge photoluminescence and enhanced LO mode multiphonon resonant Raman scattering in ZnO crystals at different temperatures. Abnormal temperature dependence of UV emission integrated intensity of ZnO and ZnO:In samples is observed. The local state emission peak of ZnO:In samples at 3.37 eV is observed in low-temperature PL spectra. The near-band-edge emission peak at room temperature was a mixture of excitons and impurity-related transitions for both of two samples.     

Ruthenium-catalyzed cyclization of 3-en-1-ynyl imines with nucleophiles via tandem 5-exo-dig cyclization and nucleophilic addition

Treatment of 3-en-1-ynyl imines with TpRuPPh₃(CH₃CN)₂PF₆ catalyst (1 mol %) in DCE (50 °C, 6 h) effected catalytic cyclization with suitable nucleophiles and gave functionalized pyrroles in good yields. The reaction mechanism is proposed to proceed via (2-pyrrolyl)carbenoid intermediates derived from 5-exo-dig cyclization. This catalytic reaction works well with various nucleophiles, including water, alcohols and anilines.     

Liquid–paper interactions during liquid drop impact and recoil on paper surfaces

The spreading and recoiling of water drops on several flat and macroscopically smooth model surfaces and on sized paper surfaces were studied over a range of drop impaction velocities using a high-speed CCD camera. The water drop spreading and recoiling results on several model hydrophobic and hydrophilic surfaces were found to be in agreement with observations reported in the literature. The maximum drop spreading diameter for those model surfaces at impact was found to be dependent upon the initial drop kinetic energy and the degree of hydrophobicity/hydrophilicity of the surface. The extent of the maximum drop recoiling was found to be much weaker for hydrophilic substrates than for hydrophobic substrates. Sized papers, however, showed an interesting switch of behaviour in the process of water drop impaction. They behave like a hydrophobic substrate when a water drop impacts on it, but like a hydrophilic substrate when water drop recoils. Although the contact angle between water and hydrophilic or hydrophobic non-porous surfaces changes from advancing to receding as reported in literature, the change of contact angle during water impact on paper surface is unique in that the level of sizing was found to have a smaller than expected influence on the degree of recoil. Atomic force microscopy (AFM) was used to probe fibres on a sized filter paper surface under water. The AFM data showed that water interacted strongly with the fibre even though the paper was heavily sized. Implications of this phenomenon were discussed in the context of inkjet print quality and of the surface conditions of sized papers. Results of this study are very useful in the understanding of inkjet ink droplet impaction on paper surfaces which sets the initial condition for ink penetration into paper after impaction.     

Synthesis, crystal structure and magnetic property of a new nickel selenite chloride: Ni5(SeO3)4Cl2

The new nickel selenite chloride, Ni₅(SeO₃)₄Cl₂, was obtained by high-temperature solid state reaction of NiCl₂, Ni₂O₃ and SeO₂ in a 1:2:4 molar ratio at 700 °C in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. Ni₅(SeO₃)₄Cl₂ crystallizes in the triclinic system, space group P-1 (No. 2) with cell parameters of a=8.076(2), b=9.288(2), c=9.376(2) Å, α=101.97(3), β=105.60(3), γ=91.83(3)° and Z=2. All nickel(II) ions in Ni₅(SeO₃)₄Cl₂ are octahedrally coordinated by selenite oxygens or/and chloride anions (([Ni(1)O₅Cl], [Ni(2)O₄Cl₂], [Ni(3)O₅Cl], [Ni(4)O₆] and [Ni(5)O₄Cl]). The structure of the title compound features a condensed three-dimensional (3D) network built by Ni(II) ions interconnected by SeO₃²⁻ anions as well as Cl⁻ anions. Magnetic property measurements show strong antiferromagnetic interaction between nickel(II) ions.     

Anomalies and curvature ofW manifolds

We study the holomorphic structure of certain complex manifolds associated withW algebras, namely, the flag manifoldsW /T andW ₁₊/T ₁₊, and the spacesW /SL(),R) andW ₁₊/GL(,R), whereT andT ₁₊ are the maximal tori inW andW ₁₊. We compute their Ricci curvature and show how the results are related to the anomaly-freedom conditions forW andW ₁₊. We discuss the relation of these manifolds with extensions of universal Teichmüller space.Supported in part by the U.S. Department of Energy, under grant DE-AS05-81ER40039Supported in part by the U.S. Department of Energy, under grant DE-FG03-84ER40168