Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.     

Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without beta-hydride elimination.     

High-power laser interactions with nanostructured materials

We use short-pulse high-power lasers to selectively modify the structure of nanolaminates and nanocrystals. It is demonstrated that femtosecond pulses can achieve excellent results for microscopic thin film removal. Laser pulses can also be used to modify the crystal structure of thin films. It is also demonstrated that coherent laser excitation promotes a selective modification of nanocrystals, resulting in changes of size, shape, and crystal structure. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +1-414/229-5589, E-mail: yakovlev@uwm.edu     

Synthesis and isomerization of conjugated oligomers containing azoimidazole unit

The Suzuki (for O1 – O3 ) and Stille (for O4 ) coupling polymerization of 2‐(phenylazo)imidazole bearing the benzyl protecting group at the 1‐position gave conjugated oligomers. The transformation from the neutral imidazole in the conjugated oligomer O2 , consisted of the alternating 2,5‐didecyl‐1,4‐phenylene unit, to the cationic imidazolium salt O2S was performed. Depending on the chemical structure of coupling partners, the absorption maximum of conjugated oligomers showed red shift or blue shift from that of the model compound M with the benzene ring at the 4,5‐positions. The absorption maximum wavelength of the cationic conjugated oligomer O2S showed a blue shift from that of the neutral conjugated oligomer O2 . The trans‐to‐cis photoisomerization of the azoimidazole unit in conjugated oligomers was observed by irradiating the light at 436 nm, and the conversion degree to the cis structure had a rough correlation with the maximum absorption wavelength of materials. The trans‐to‐cis photoisomerization in the film state was sluggish. On the other hand, the cis‐to‐trans thermal isomerization of the azoimidazole unit was confirmed and the absorbance returned to the initial state before the photoisomerization. The trans‐to‐cis photoisomerization of the cationic conjugated oligomer O2S required large energy, and the prolonged light irradiation might decompose the azoimidazole unit. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Molecular orientation and mechanical anisotropy of polypropylene sheet containing N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide

Effect of mixing and processing conditions at T‐die extrusion on the structure and mechanical properties is studied for isotactic polypropylene (PP) containing a small amount of β‐form nucleating agent, N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide. It is found that trigonal β crystals are predominantly formed in the extruded samples containing the nucleating agent irrespective of the mixing and processing conditions, leading to the marked mechanical toughness. On the contrary, the molecular orientation is significantly affected by the mixing and processing conditions. In particular, it should be noted that PP molecules in the extruded sheet which was mixed at high temperature (260 °C) and extruded at low temperature (200 °C) orient perpendicular to the applied flow direction. As a result, the sheet shows anomalous mechanical anisotropy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 424–433, 2009     

Highly efficient substitution of allylic picolinates with copper reagents derived from aryl-, alkenyl-, furyl-, and thienyl-lithiums

Substitution of optically active allylic picolinate, cis R¹-CH(OC(O)(2-Py))CHCHR² (R¹=(CH₂)₂Ph, R²=CH₂OTBS), with phenylcopper reagents derived from salt free PhLi (2 equiv) and CuBr·Me₂S (2 and 1 equiv, respectively) was highly promoted by MgBr₂ (3 equiv), producing anti S_N2′ product regio- and stereoselectively. This reagent system was proven to be general with several picolinates (R¹, R²: Ph(CH₂)₂, PMBO(CH₂)₃, Me, TBSOCH₂, PMBOCH₂, c-Hex). Furthermore, aryl copper reagents prepared from ArLi, which was in turn prepared by Li-halogen exchange, was proven to be compatible with the substitution in the presence of larger quantity of MgBr₂ than that of LiX coproduced by the exchange. Substitution was not interfered with the steric hindrance on aryl coppers (Ar: 2-MeOC₆H₄, 2,6-(MOMO)₂-4-MeC₆H₂, 2,6-Me₂C₆H₃, etc.). Similarly, stereodefined cis and trans alkenyl, furyl, and thienyl reagents gave the corresponding anti S_N2′ products efficiently.     

Efficient decoherence-free entanglement distribution over lossy quantum channels

We propose and demonstrate a scheme for boosting the efficiency of entanglement distribution based on a decoherence-free subspace over lossy quantum channels. By using backward propagation of a coherent light, our scheme achieves an entanglement-sharing rate that is proportional to the transmittance T of the quantum channel in spite of encoding qubits in multipartite systems for the decoherence-free subspace. We experimentally show that highly entangled states, which can violate the Clauser-Horne-Shimony-Holt inequality, are distributed at a rate proportional to T.     

Impact of dispersion on amplitude and frequency noise in a Yb-fiber laser comb

We describe a Yb-fiber-based laser comb, with a focus on the relationship between the net-cavity dispersion and frequency noise on the comb. While tuning the net-cavity dispersion from anomalous to normal, we measure the relative intensity noise, offset frequency (f(CEO)) linewidth, and the resulting frequency noise spectrum on the f(CEO). We find that the laser operating at zero net-cavity dispersion has many advantages, including an approximately 100× reduction in free-running f(CEO) linewidth and frequency noise power spectral density when compared to the normal-dispersion regime. At the zero-dispersion point, we demonstrate a phase-locked f(CEO) beat with low residual noise.