Oligo(phenylene vinylene)-poly(methylstyrene) hybrids: controlled step-wise molecular wiring of oligo(phenylene vinylene)

Well defined oligo(phenylene vinylene) grafted polymers known as oligo(phenylene vinylene)-poly(methylstyrene) hybrids have been developed using a step-wise synthetic protocol, where the length of the OPV can be controlled systematically to achieve specific optoelectronic properties. The process allows the structural modification of attached OPV at a molecular level either by varying the chain length or by changing functionalities. The step-wise generation of OPV chains on the backbone of a highly soluble polymer ensures solubilization in a variety of solvents and also the exhibition of interesting optical properties.     

Synthesis and characterization of new blue‐light‐emitting polymers based on PPP and PPV having fluorene pendant at vinyl bridge

The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m‐phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m‐phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed, synthesized, and characterized. The obtained polymers showed weight‐average molecular weights of 11,100–39,800 with polydispersity indexes ranging from 1.5 to 2.1. The resulting polymers were amorphous with high thermal stability and readily soluble in common organic solvents. The obtained polymers showed blue emission (λ_max = 456–475 nm) in PL spectra, and polymer 4 containing terphenylene vinylene m‐phenylene vinylene showed the most blue shifted blue emission (λ_max = 456 nm). The double layer light‐emitting diode devices fabricated by using obtained polymers as emitter emitted bright blue light. The device showed turn on voltage around 6.5 V and brightness of 70–250 cd/m². © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4923–4931, 2006     

Synthesis of conjugated copolymers containing phenothiazinylene vinylene moieties and their electrooptic properties

Four different types of conjugated copolymers, consisting of alternating structures of phenothiazinylene vinylene and phenylene vinylene derivatives such as phenylene vinylene, 1,1′‐biphenyl‐4,4′‐ylene vinylene, 2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene, and 9,10‐anthrylene vinylene, were prepared by Horner–Emmons condensation between appropriate diphosphonates and dialdehydes. Single‐layer and double‐layer light‐emitting diodes were fabricated with the synthesized conjugated polymers, and their electroluminescent properties were investigated. Poly(N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐9,10‐anthrylene vinylene), containing phenothiazinylene vinylene and anthrylene vinylene as repeat units, emitted a reddish‐orange color with Commission Internationale de l'Eclairage coordinates of x = 0.6173 and y = 0.3814 that was very similar to the National Television System Committee standard red, and it showed a bipolar carrier‐injection/transporting capability caused by electron‐withdrawing anthracene and electron‐donating amino groups. Poly[N‐2‐ethylhexyl‐3,6‐phenothiazinylene vinylene‐alt‐2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylene vinylene], containing phenothiazinylene vinylene and dialkoxy phenylene vinylene moieties, showed excellent hole‐injection/transporting capability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2502–2511, 2003     

Study of the aggregation behavior of a π-conjugated dendrimer with a twisted core

A dendrimer having phenylene vinylene and phenylene ethynylene moieties, a twisted core, and eighteen chiral centers on the periphery has been prepared in high yield by using Sonogashira and Horner–Wadsworth–Emmons reactions. UV–visible and fluorescence spectra and circular dichroism measurements have been envisaged to study the aggregation behavior.     

Self-assembly and micellization of amphiphilic rod-coil block oligomer at the mica-water interface

In this paper, in situ atomic force microscopy has been used to investigate the micellization and self-assembling structure of an amphiphilic rod-coil block oligomer (EO16OPV) containing a conjugated oligo(phenylene vinylene) dimer and poly(ethylene oxide) at the mica-water interface. It is found that EO16OPV molecules have strong adsorption and aggregation properties on mica. In the wide concentration range from above the critical micelle concentration (cmc) to far below the cmc, a closely packed layer of stripe-like micelles with two preferred orientations can be formed at the mica-water interface. A cylindrical micelle structure for the stripes is proposed. We demonstrate that the stripe-like micelles formed on mica originate from different micellization processes at solution concentrations above and below the cmc. The origins of the strong micellization properties and oriented arrangement of the stripes are also discussed.     

Density functional crystal orbital study of cyano‐substituted poly(para‐phenylene‐vinylene) and poly(quinoxaline‐vinylene)

We have calculated the optical and electronic properties of several conjugated organic polymers: poly(p‐phenylene‐vinylene) (PPV) and its derivatives. Cyano substitutions on the phenylene ring: poly(2,5‐dicyano‐p‐phenylene‐vinylene) (2,5‐DCN‐PPV) and on the vinylene linkage: poly(p‐phenylene‐7(,8)‐(di)cyano‐vinylene) are considered. In addition, poly(quinoxaline‐vinylene) (PQV) is studied. The infinite isolated quasi‐1D chains are treated with periodic boundary conditions, using atomic basis sets. In a comparative study of PPV, some issues regarding the selection of the functionals and basis sets are discussed and excitation energies derived from time‐dependent and from ordinary methods are compared. It is concluded that for these polymers the calculations are informative at the B3LYP/6‐31G** density functional theory (DFT) level. The absolute values might change with improved methods, but the similarity of the polymers suggests that the relative characterization is adequate. Band structures are communicated along with characteristics of the highest occupied and the lowest unoccupied crystal orbitals (HOCO and LUCO). Electron affinities, ionization potentials, valence and conduction bandwidths, and effective masses at the bandgap are given. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Self-assembly of bipolar amphiphiles

Over the past 2 years, various symmetrical and unsymmetrical bipolar amphiphiles (bolaamphiphiles) have been synthesized to study their self-organizing and packing properties alone as well as in mixtures with conventional amphiphiles. This review focuses on the lyotropic properties of these bolaamphiphiles and describes their in some cases quite unusual supramolecular self-assembling properties in aqueous media and at the air–water and liquid–solid interface.     

Molecular engineering of organic sensitizers containing p-phenylene vinylene unit for dye-sensitized solar cells

Three organic sensitizers containing bis-dimethylfluorenyl amino donor and a cyanoacrylic acid acceptor bridged by p-phenylene vinylene unit were synthesized. The power conversion efficiency was quite sensitive to the length of bridged phenylene vinylene groups. A nanocrystalline TiO2 dye-sensitized solar cell was fabricated using three sensitizers. The maximum power conversion efficiency of JK-59 reached 7.02%.     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

可溶性聚对苯乙炔衍生物的合成

聚对苯乙炔（ＰＰＶ）具有独特的光电性能,经强氧化剂掺杂后是一类重要的导电材料［１］,而且具有良好的非线性光学（ＮＬＯ）性质［２］,也是目前性能最好的高分子电致发光材料［３,４］．可溶性的ＰＰＶ衍生物有望在显示领域广泛应用,从而成为电致发光领域研究的新...     

The suzuki–heck polymerization as a tool for the straightforward obtainment of poly(fluorenylene‐vinylene) sensitizers for dye‐sensitized solar cells

This article describes the synthesis and properties of the first poly(arylene‐vinylene)‐based sensitizers for application in dye‐sensitized solar cells (DSSC). The polymers were prepared by the Suzuki–Heck copolymerization of potassium vinyltrifluoroborate (PVTB) with a mixture of dibromoaryl comonomers designed to obtain macromolecules able to bind onto the photoelectrode by means of carboxyphenylene units. The copolymerization reactions were carried out in the presence of an excess of PVTB to lower the molecular weights of the polymers, which were obtained as soluble materials. The polymers poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene] ( P1 ), poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐(4,7‐benzothiadiazolylene)‐vinylene] ( P2 ), and poly[(9,9‐didodecyl‐2,7‐fluorenylene)‐vinylene‐co‐(carboxy‐2,5‐phenylene)‐vinylene‐co‐2,5‐thienylene‐vinylene] ( P3 ) were used in DSSC devices, obtaining conversion efficiencies up to 0.88% ( P3 ). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Metabolically Active,Fully Hydrolysable Polymersomes

The synthesis and aqueous self‐assembly of a new class of amphiphilic aliphatic polyesters are presented. These AB block polyesters comprise polycaprolactone (hydrophobe) and an alternating polyester from succinic acid and an ether‐substituted epoxide (hydrophile). They self‐assemble into biodegradable polymersomes capable of entering cells. Their degradation products are bioactive, giving rise to differentiated cellular responses inducing stromal cell proliferation and macrophage apoptosis. Both effects emerge only when the copolymers enter cells as polymersomes and their magnitudes are size dependent.     

Metabolically Active,Fully Hydrolysable Polymersomes

The synthesis and aqueous self‐assembly of a new class of amphiphilic aliphatic polyesters are presented. These AB block polyesters comprise polycaprolactone (hydrophobe) and an alternating polyester from succinic acid and an ether‐substituted epoxide (hydrophile). They self‐assemble into biodegradable polymersomes capable of entering cells. Their degradation products are bioactive, giving rise to differentiated cellular responses inducing stromal cell proliferation and macrophage apoptosis. Both effects emerge only when the copolymers enter cells as polymersomes and their magnitudes are size dependent.     

Synthesis and electrical conductivity of poly(arylene vinylene). I. Poly(2,5-dimethoxyphenylene vinylene) and poly(2,5-dimethylphenylene vinylene)

The highly conjugated aromatic polymers, poly(2,5-dimethoxyphenylene vinylene) and poly(2,5-dimethylphenylene vinylene), were obtained from their water soluble, sulfonium salt precursor polymers. Films of these polymers were reacted with either AsF₅ or I₂ vapor. Poly(2,5-dimethoxyphenylene vinylene) showed increases in electrical conductivity of up to 14 to 15 orders of magnitude for these two dopants, while an 8 to 9 order of magnitude increase was observed for poly(2,5-dimethylphenylene vinylene) with the same dopants. The synthesis of the precursor polymers, the properties and elimination reactions of films of the precursors, the doping reactions, and the conductivities of the resulting phenylene vinylene films are discussed.     

Synthesis,Electrochemical, and Optical Properties of a Novel PPV/PPE Block‐Copolymer

Summary: A novel poly(p‐phenylene vinylene) (PPV)/poly(p‐phenylene ethynylene) (PPE) block‐copolymer was synthesized by a cross‐coupling polycondensation with Pd(PPh₃)₂Cl₂ and a phase‐transfer catalyst, and was confirmed by ¹H NMR and IR spectroscopy and elemental analysis. The thermal, electrochemical, and photoluminescent properties of the new copolymer have been investigated. The incorporation of triple bonds into the cyano‐substituted PPV (CN‐PPV) backbone leads to higher oxidation and reduction potentials than poly(2‐methoxy‐5‐(2‐ethylhexyloxy)‐p‐phenylene vinylene) (MEH‐PPV) and CN‐PPV, potentially making the copolymer a good electron‐transporting material for use in a light‐emitting‐diode device.

The cyclic voltammogram of the novel poly(p‐phenylene vinylene) (PPV)/poly(p‐phenylene ethynylene) (PPE) block‐copolymer synthesized here.     

Phase diagram for assembly of biologically-active peptide amphiphiles

We construct a phase diagram for self-assembling biologically active peptide amphiphiles. The structure and stability of the assemblies are studied as a function of pH and salinity of the solution. The general features of the phase diagram are predicted based on theoretical modeling of the self-assembly process, as well as experimental data, and further experiments are performed to verify and ascertain the boundary locations of the diagram. Depending on solution conditions, the amphiphiles can form cylindrical or spherical micelles, intermediate structures between these, or may not assemble at all. We also demonstrate that changing conditions may result in phase transitions among these structures. This type of phase diagram could be useful in the design of certain supramolecular nanostructures by providing information on the necessary conditions to form them.     

One‐Step Synthesis of [16]Helicene

A single‐strand arylene–vinylene precursor containing four phenylene and three naphthylene units linked together with six vinylene spacers undergoes helical folding via sextuple photocyclization to give a [16]helicene core in a single step. The phenylene and naphthylene units are arranged in the precursor such that unfavorable side reactions (anthracene or benzoperylene formation) are avoided, and this is the key to the success of the one‐step synthesis of [16]helicene, which is the longest [n]helicene that has been synthesized to date.     

Self-assembling peptide scaffolds for regenerative medicine

Biomaterials made from self-assembling, short peptides and peptide derivatives have great potential to generate powerful new therapies in regenerative medicine. The high signaling capacity and therapeutic efficacy of peptidic scaffolds has been established in several animal models, and the development of more complex, hierarchical structures based on peptide materials is underway. This highlight discusses several classes of self-assembling peptide-based materials, including peptide amphiphiles, Fmoc-peptides, self-complementary ionic peptides, hairpin peptides, and others. The self-assembly designs, bioactive signalling strategies, and cell signalling capabilities of these bioactive materials are reported. The future challenges of the field are also discussed, including short-term goals such as integration with biopolymers and traditional implants, and long term goals, such as immune system programming, subcellular targeting, and the development of highly integrated scaffold systems.     

A combined experimental and theoretical investigation of donor and acceptor interface in efficient aqueous-processed polymer/nanocrystal hybrid solar cells

As a route to improving the energy conversion of organic-inorganic hybrid-solar cells, we have tested the performance of poly (phenylene vinylene) (PPV), poly(2,5-thienylene vinylene) (PWTV) polymers and CdTe nanocrystal devices produced via aqueous-processing. It is found that small differences in the conformation of the sensitizer lead to dramatic effects on the solar cell efficiency. Using a combination of UV-Vis absorption spectroscopy and first-principles non-adiabatic molecular dynamics (NAMD) based on time-dependent density-functional theory (TDDFT), PPV is found to have a longer electron injection and recombination time despite seeming to have a better energy alignment with the substrate, which leads to a higher devices performance than PWTV. The present results shed new light on the understanding of organic-inorganic hybrid-solar cells and will trigger further experimental and theoretical investigations.     

Naturally Derived Silicone Surfactants Based on Saccharides and Cysteamine

Silicone surfactants are widely used in many industries and mostly rely on poly(ethylene glycol) (PEG) as the hydrophile. This can be disadvantageous because commercial PEG examples vary significantly in polydispersity—constraining control over surface activity of the surfactant—and there are environmental concerns associated with PEG. Herein, we report a three-step synthetic method for the preparation of saccharide-silicone surfactants using the natural linker, cysteamine, and saccharide lactones. The Piers–Rubinsztajn plus thiol-ene plus amidation process is attractive for several reasons: if employed in the correct synthetic order, it allows for precise tailoring of both hydrophobe and hydrophile; it permits the ready utilization of natural hydrophiles cysteamine and saccharides in combination with silicones, which have significantly better environmental profiles than PEG; and the products exhibit interesting surface activities.