Synthesis and characterization of linear tetrablock quarterpolymers of styrene,isoprene, dimethylsiloxane,and 2-vinylpyridine

A series of five tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine with molecular weights varying from 117 × 10³ to 177 × 10³ and having different compositions were synthesized. The synthesis was based on recent advances in the controlled high-vacuum anionic polymerization of hexamethylcyclotrisiloxane and on the selective linking of poly(dimethylsiloxane)lithium with the chlorosilane group of the heterofunctional linking agent chloromethylphenylethylene dimethylchlorosilane. Combined characterization results by size exclusion chromatography, membrane osmometry, and NMR spectroscopy suggested that the synthesized multiblock multicomponent polymers had a high degree of structural and compositional homogeneity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 514–519, 2004     

Synthesis and characterization of model 3‐miktoarm star copolymers of poly(dimethylsiloxane) and poly(2‐vinylpyridine)

3‐Miktoarm star copolymers, 3μ‐D₂V, with two poly(dimethylsiloxane) (PDMS) and one poly(2‐vinylpyridine) (P2VP) arm, were synthesized by using anionic polymerization–high vacuum techniques and (chloromethylphenylethyl)methyl dichlorosilane, heterofunctional linking agent, with two SiCl groups and one CH₂Cl group. The synthetic strategy involves the selective reaction of the two ? SiCl groups with PDMSOLi living chains, followed by reaction of the remaining chloromethyl group with P2VPLi. Combined molecular characterization results (size exclusion chromatography, membrane osmometry, and ¹H NMR spectroscopy) revealed a high degree of structural and compositional homogeneity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 614–619, 2006     

Synthesis of polycyclic pyrazoles through formation of the first fused heterocyclic o-quinodimethane intermediate

1-Benzoyl-4,6-dibromo-3-methyl-1,4,5,6-tetrahydrocyclopenta[c]pyrazole (2) was used as a precursor for o-quinodimethane 3, which was trapped by in situ reactions with dienophiles to give bridged pyrazole derivatives.     

A flow-through microfluidic chip for continuous dielectrophoretic separation of viable and non-viable human T-cells

Effective methods for rapid sorting of cells according to their viability are critical in T cells based therapies to prevent any risk to patients. In this context, we present a novel microfluidic device that continuously separates viable and non-viable T-cells according to their dielectric properties. A dielectrophoresis (DEP) force is generated by an array of castellated microelectrodes embedded into a microfluidic channel with a single inlet and two outlets; cells subjected to positive DEP forces are drawn toward the electrodes array and leave from the top outlet, those subjected to negative DEP forces are repelled away from the electrodes and leave from the bottom outlet. Computational fluid dynamics is used to predict the device separation efficacy, according to the applied alternative current (AC) frequency, at which the cells move from/to a negative/positive DEP region and the ionic strength of the suspension medium. The model is used to support the design of the operational conditions, confirming a separation efficiency, in terms of purity, of 96% under an applied AC frequency of 1.5 × 10⁶ Hz and a flow rate of 20 μl/h. This work represents the first example of effective continuous sorting of viable and non-viable human T-cells in a single-inlet microfluidic chip, paving the way for lab-on-a-chip applications at the point of need.     

Dynamical disorder of spin-induced Jahn-Teller orbitals with the insulator-metal transition in cobaltites

Using elastic and inelastic neutron scattering, we investigated the evolution of the local atomic structure and lattice dynamics of La(1-x)SrxCoO3 (x=0-0.5) as it crosses over with x from an insulator to a ferromagnetic metal (FMM). Our pair density function analysis indicates that, in the paramagnetic insulating phase for all x, spin activation of Co3+ ions induces local static Jahn-Teller (JT) distortions. The size of the JT lattice increases almost linearly with x. However, in the FMM phase, static JT distortions are absent for x< or =30%. This coincides with narrowing of variant Planck's constant over 2 pi omega=22 and 24 meV modes in the phonon spectrum which we argue is due to localized dynamical JT fluctuations. For x>30%, static JT distortions reappear along with broadening of the phonon modes because of weakened charge-lattice interactions.     

Linear pentablock quintopolymers (l‐SIDMV) with five incompatible blocks: Polystyrene,polyisoprene‐1,4, poly(dimethylsiloxane), poly(tert‐butyl methacrylate), and poly(2‐vinylpyridine)

Three linear pentablock quintopolymers (l‐SIDMV), where S is polystyrene (PS), I polyisoprene‐1,4 (PI), D poly(dimethylsiloxane) (PDMS), M poly(tert‐butyl methacrylate) (PtBuM), and V poly(2‐vinylpyridine) (P2VP), were synthesized by anionic polymerization high vacuum techniques. The approach involves the following: (a) The synthesis of living triblock terpolymer PS‐b‐PI‐b‐PDMSLi and diblock copolymer P2VP‐b‐PtBuMK by sequential polymerizations of the corresponding monomers with sec‐BuLi and benzyl potassium, respectively; and (b) The selective linking of the living triblock terpolymer with the chlorosilane group of 2‐(chloromethylphenyl)ethyldimethylchlorosilane (CMPDMS), followed by linking of the living block copolymer with the remaining chloromethyl group of CMPDMS. Molecular characterization carried out by size exclusion chromatography, membrane osmometry, solution (in CDCl₃ or d₈‐toluene) and solid‐state ¹H‐NMR spectroscopy indicated a high degree of molecular and compositional homogeneity. Differential scanning calorimetry results on the precursors and final polymers were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3938–3946, 2008     

In search for mixed transition metal/lanthanide single-molecule magnets: Synthetic routes to NiII/TbIII and NiII/DyIII clusters featuring a 2-pyridyl oximate ligand

Employing the mononuclear complex [Ni{(py)C(Me)NO}₂{(py)C(Me)NOH}] (1) as ‘ligand’ [(py)C(Me)NOH = methyl 2-pyridyl ketone oxime], the use of the ‘metal complexes as ligands’ approach has led to the synthesis of the mixed Ni^II/Ln^III complexes [NiTb{(py)C(Me)NO}₂(NO₃)₃{(py)C(Me)NOH}] (2), [Ni₂Ln₂{(py)C(Me)NO}₆(NO₃)₄] (Ln = Dy, 3; Ln = Tb, 4) and [Ni₂Tb{(py)C(Me)NO}₆](NO₃) (5). The structures of 2, 3, and 5, and the magnetic properties of 2 and 5 are briefly discussed.     

Possible link of a structurally driven spin flip transition and the insulator-metal transition in the perovskite La(1-x)Ba(x)CoO3

The nature of the magnetic ground state near the insulator-metal transition (IMT) in La(1-x)Ba(x)CoO3 was investigated via neutron scattering. Below the critical concentration, x(c)～0.22, a commensurate antiferromagnetic (AFM) phase appears initially. Upon approaching x(c), the AFM component weakens and a ferromagnetic (FM) ordered phase sets in while in the rhombohedral lattice. At x(c), a spin flip to a new FM structure occurs at the same time as the crystal symmetry transforms to orthorhombic (Pnma). The Pnma phase may be the driving force for the IMT.