Synthesis and electro‐optical properties of polyfluorene modified with randomly distributed electron‐donor and rotaxane electron‐acceptor structural units in the main chain

Polyfluorene PF?γCD rotaxane copolymer, composed of randomly distributed 9,9‐dioctylfluorene, methyltriphenylamine (electron‐donating) and 9‐dicyanomethylenefluorene complexed with γ‐cyclodextrin (γCD) (electron‐accepting) structural units, has been synthesized by Suzuki cross‐coupling reaction. The chemical structures were proved by FTIR and ¹H NMR spectroscopy. The surface morphology, thermal, optical, electrochemical behavior, and adhesion characteristics of the obtained rotaxane copolymer have been investigated and compared with those of the nonrotaxane counterpart ( PF ). Relatively high fluorescence efficiency, almost identical normalized absorbance maximum in solution and solid‐state of PF?γCD rotaxane copolymer, and a more uniform and smoother surface with lower adhesion forces provides the role of γCD encapsulation on the lower aggregation propensity. PF?γCD and PF copolymers exhibit n‐ and p‐doping processes and blue‐light emission in the film state. The optical and electrochemical band gaps (ΔE_g), as well as the highest occupied molecular orbital/lowest unoccupied molecular orbital positions in an energetic diagram indicate that both copolymers are promising blue‐emitting electroluminescent materials. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Inversion Properties of n-Alkane Phosphonic Acids Stabilized Emulsions: HLB Dependence

The emulsifier properties of n-alkane phosphonic acids (C10H21PO3H2; C12H25PO3H2 and C13H27PO3H2) and their mono- and di-sodic salts were studied, with emphasis on the morphological and dynamical inversion properties as a function of their neutralization degree. Maximum stabilization properties were appreciated for C10PO3H2 and C12PO3H2 while not for C13PO3H2. Such fact is associated to their odd number of carbon atoms chain, which is the origin of the intrachain constraints on the tail-chain flexibility.     

Thermoresponsive super water absorbent hydrogels prepared by frontal polymerization

Frontal polymerization was used as an alternative technique for the preparation of super water absorbent hydrogels obtained from acrylamide and 3‐sulfopropyl acrylate, potassium salt (SPAK) in the presence of N,N′‐methylene‐bisacrylamide as a crosslinker. All samples were synthesized in dimethyl sulfoxide, and their swelling behavior in water was investigated. It was found that their features are dependent on the monomer ratio used, which influenced the porous morphology, and consequently, the swelling capability. The swelling ratio ranges from about 1000% for the acrylamide homopolymer up to 14,000% for the sample containing 87.5 mol % of SPAK, thus indicating that this parameter can be easily tuned by using the appropriate monomer ratio. The affinity towards water was eventually confirmed by contact angle analysis. Polymer hydrogels made from at least 62.5 mol % SPAK exhibit a thermoresponsive behavior, with a lower critical solution temperature of ～30 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2486–2490, 2010     

Capillary zone electrophoretic separation of cyclodextrins with indirect UV photometric detection

A method for the separation of cyclodextrins by capillary zone electrophoresis with indirect detection is described. It is based on the formation of inclusion complexes with benzoate which simultaneously forms a UV absorbing constituent of the background electrolyte used for the separation.     

Structure and shear orientation of a side chain liquid crystal polymer studied by small angle X-ray scattering

We have studied the structure and shear flow behaviour of a side chain liquid crystal polymer, namely P₁₂, in the smectic (SmA_d) phase. Simultaneous oscillatory shear and small angle X-ray scattering experiments showed that, as expected, the shearing of P₁₂ at high frequency and large strain amplitudes leads to the alignment of the smectic layer normals parallel to the neutral direction. It was also found that, on erasing the memory of the prior shear alignment through melting, P₁₂ can unexpectedly orient with the smectic layers perpendicular to the shear flow direction (b-configuration). We speculate that the b-configuration is adopted due to a counter-balance between the rather long spacer in P₁₂ which decouples mesogens from the backbone, and the oscillatory character of the shear applied to P₁₂.     

Inner solvers for interior point methods for large scale nonlinear programming

This paper deals with the solution of nonlinear programming problems arising from elliptic control problems by an interior point scheme. At each step of the scheme, we have to solve a large scale symmetric and indefinite system; inner iterative solvers, with an adaptive stopping rule, can be used in order to avoid unnecessary inner iterations, especially when the current outer iterate is far from the solution. In this work, we analyse the method of multipliers and the preconditioned conjugate gradient method as inner solvers for interior point schemes. We discuss the convergence of the whole approach, the implementation details and report the results of numerical experimentation on a set of large scale test problems arising from the discretization of elliptic control problems. A comparison with other interior point codes is also reported. This research was supported by the Italian Ministry for Education, University and Research (MIUR) projects: FIRB Project: “Parallel Nonlinear Numerical Optimization PN ² O” (grant n. RBAU01JYPN, ) and COFIN/PRIN04 Project “Numerical Methods and Mathematical Software for Applications” (grant n. 2004012559, ).     

On the solution of indefinite systems arising in nonlinear programming problems

This work is concerned with the convergence properties and the numerical analysis of the preconditioned conjugate gradient (PCG) method applied to the solution of indefinite linear systems arising in nonlinear optimization. Our approach is based on the choice of quasidefinite preconditioners and of a suitable factorization routine. Some theoretical and numerical results about these preconditioners are obtained. Furthermore, we show the behaviour of the PCG method for different formulations of the indefinite system and we compare the effectiveness of the proposed variants. Copyright © 2007 John Wiley & Sons, Ltd.     

Production of the Bengamide Class of Marine Natural Products in Myxobacteria: Biosynthesis and Structure–Activity Relationships

The bengamides, sponge‐derived natural products that have been characterized as inhibitors of methionine aminopeptidases (MetAPs), have been intensively investigated as anticancer compounds. We embarked on a multidisciplinary project to supply bengamides by fermentation of the terrestrial myxobacterium M. virescens, decipher their biosynthesis, and optimize their properties as drug leads. The characterization of the biosynthetic pathway revealed that bacterial resistance to bengamides is conferred by Leu 154 of the myxobacterial MetAP protein, and enabled transfer of the entire gene cluster into the more suitable production host M. xanthus DK1622. A combination of semisynthesis of microbially derived bengamides and total synthesis resulted in an optimized derivative that combined high cellular potency in the nanomolar range with high metabolic stability, which translated to an improved half‐life in mice and antitumor efficacy in a melanoma mouse model.