A novel pyrrolidinyl PNA showing high sequence specificity and preferential binding to DNA over RNA

A novel conformationally constrained pyrrolidinyl peptide nucleic acid (PNA) carrying an D-aminopyrrolidine carboxylic acid (D-Apc) spacer was synthesized, and its interactions with complementary oligo- and polynucleotides were studied by UV and CD spectroscopy. The decathymine PNA formed very stable PNA-DNA complexes with poly(dA) and (dA)(10) by a sequence-specific A-T pairing. The interaction with poly(rA) gave the corresponding PNA-RNA complex with much lower stability.     

Synthetic approaches to new polymers

A plenary lecture should be an introduction into the main topic of the symposium and a review about the state of art. Therefore, in the first part of this presentation different possibilities for the preparation of new polymers are briefly discussed from a chemical point of view. Some selected examples from the literature show how methods of organic chemistry can be utilized for polymer science: new catalytic systems, new monomers, modification of polymers, new poly-reactions. In the second part, several polyelectrolytes are described: polymers with sec., tert. and quart. N-atoms in the main chain, block copolymers and block polyampholytes. The third part deals with the problems of rod-like macromolecules for instance oligo- and poly(p-phenylene)s, poly(p-phenyleneethynylene)s, aromatic polyimides and a new spiroionene.     

Recent advances in acetylene-based helical oligomers and polymers: Synthesis,structures, and properties

In this review, we describe the recent advances in the chemistry of helical polymers and oligomers containing acetylene units in the main chain. Owing to their great benefits such as high availability and handleability, good reactivity, rigidity, linearity, and low bulkiness, acetylene units have been utilized and incorporated in helical folding oligomers and polymers such as oligo- and poly(m-phenylene ethynylene)s. General synthetic methods as well as the structures, functions, and properties of acetylene-based helical oligomers and polymers are discussed by focusing on recent examples from 2009 to 2017.     

基于PCPDTBT复合材料的制备及光致电荷转移

合成了PCPDTBT,通过NMR,GPC等方法对聚合物进行了表征.研究了聚合物的热学与电化学性质.采用溶液法将电子给体PCPDTBT与两种电子受体1-(3-甲氧基羰基)丙基-1-苯基[6,6]C61(PCBM)和ZnO纳米粒子分别进行了复合,通过研究复合前后的荧光变化,确认了给体-受体两相界面间发生了由分子能级差引发的光致电荷转移.这些研究结果为探索性能更佳的有机太阳能电池材料体系提供了重要的参考依据.     

含二呋喃基苯并噻二唑的聚芳炔类衍生物的合成与性能

以四(三苯基磷)钯(Pd(PPh3)4)和CuI为催化剂,在二异丙胺和四氢呋喃溶液中,采用宽能带的1,4-二乙炔基-2,5-二(十二烷氧基)苯(PE)和窄能带的4,7-双(5′-溴-2′-呋喃)-2,1,3-苯并噻二唑(FBT)合成了一系列新型聚芳炔。长链烷氧基的存在使得此类聚合物在常用的有机溶剂中具有较好的溶解性和成膜性。通过对上述聚合物的紫外-可见吸收、荧光发射及循环伏安等基本性能进行探讨可知,随着共聚物中FBT含量的增加,共聚物薄膜的吸收起始波长及荧光发射波长均有明显的红移。聚合物薄膜的最大发射峰位于600～650 nm,聚合物中的能量能有效地由PE单元转移到FBT单元上。     

Biodegradable synthetic and semisynthetic polymers

As a part of our continuing interest in the preparation of multifunctional polymeric materials and evaluation of their potential in pharmaceutical, medical and environmental fields, a survey on new polymeric systems of synthetic and semisynthetic origin, susceptible to bioerosion and/or biodegradation attack is presented. In particular, attention has been focused on the design, preparation and characterization of the following classes of hydrophilic and/or water-soluble polymeric materials: hydroxyl-containing poly(ester)s, hydroxyl-containing poly(amide)s, hydrophilic polymers containing carboxylic groups, perhydroxylated oligo- and poly(saccharide)s, oxidized poly(saccharide)s, and hybrid polymeric materials based on blends of carboxyl-containing synthetic polymers and proteins. The rationale of the research activity undertaken over the years is illustrated by focusing on some specific achievements of practical significance.     

A new simple synthesis of poly(thiophene-methine)s

Acid-promoted polycondensation of 3,4-(ethylenedioxy)thiophene-2-carbaldehyde leads to a conjugated heavily p-doped poly(thiophene-methine), which can be dedoped leading to a low band-gap neutral polymer.     

Synthesis and Characterization of Small Band-gap Conjugated Polymers - Poly(pyrrolyl methines)

A kind of small band-gap conjugated polymers-poly (pyrrolyl methines) and their precursors-(poly pyrrolyl methanes) have been synthesized by a simple method and characterized by 1HNMR, FT-IR, TGA and UV-Vis. These polymers can be dissolved in high polar solvents such as DMSO, DMF or NMP. The results reveals that the band-gap of the synthesized conjugated polymers are in the range of 0.96～1.14 eV and they all belong to the small band-gap polymers. The conductivity of doped products with iodine is in the range of semiconductor.     

Comparison of physical-mechanical features of polyethylene based polymers employed as sealants in solar cells

In this article, we compared the sealing strength, flexibility, thermal stability, and moisture-barrier properties of two polymeric films, both based on linear low density poly ethylene (LLDPE), which can be successfully used as sealant materials in electrical devices. One example is the dye-sensitized solar cell (DSSC), a low-cost third generation device, based on a photo-electrochemical system. Characterization of LLDPE modified with maleic anhydride (PE-MAH) or with ionomeric ethylene-acrylic acid co-polymer (EMAA) was carried out. Results highlighted as PE-MAH exhibits better adhesion features toward glass, higher thermal stability, and lower wet ability even at high temperatures (80?°C) compared to EMAA. Sealant’s features have been correlated to their chemical and structural composition.     

Synthesis and Characterization of Oligo(2,7-biphenylenylene-(E)-vinylene)s: Conjugated Oligomers Containing Antiaromatic 12-π Electron Units

The syntheses and the electronic properties of oligo(2,7-biphenylenylene-(E)-vinylene)s are reported. According to our spectral analysis, a limit of 2.5 ev for the peak band-gap of poly(2,7-biphenylenylene-(E)-vinylene)s is estimated. In addition, we discovered that oligo(2,7-biphenylenylene-(E)-vinylene)s are amphoteric and can be either oxidized or reduced electrochemically.     

Steps to demarcate the effects of chromophore aggregation and planarization in poly(phenyleneethynylene)s. 1. Rotationally interrupted conjugation in the excited states of 1,4-bis(phenylethynyl)benzene.

A series of photophysical measurements and semiempirical calculations were carried out with 1,4-bis(phenylethynyl)benzene in search of evidence on the effects of phenyl group rotation and chromophore aggregation of oligo- and poly(phenyleneethynylene)s. It is suggested that planarization gives rise to relatively modest shifts of ca. 20-30 nm, which preserve the vibronic structure of the monomer and retain a high emission quantum yield. In contrast, it is proposed that aggregation gives rise to larger shifts and loss of vibronic structure.     

一种新型低带隙共轭聚合物的合成及其光学性质

在钯催化剂作用下, 通过4,7-二(5-溴-2-噻吩基)[2,1,3]苯并噻二唑与2,5-二乙炔基-3-辛基噻吩的偶联反应, 合成了一种新的共轭高分子聚4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔(PTE-DTBT). 通过紫外可见吸收光谱及荧光光谱对其光学性质进行了研究. 紫外-可见吸收谱结果表明, PTE-DTBT的固体膜光学带隙为1.71 eV; 电化学测试其带隙为1.88 eV. TiO₂/PTE-DTBT共混固体膜的荧光发射谱结果表明电子供体PTE-DTBT分子与电子受体TiO₂分子间存在有效的电子转移.     

SYNTHESIS AND CHARACTEAIZATION OF POLY(PYRROLY METHINE)

A novel small band-gap conjugated polymer - poly [(3-acetylpyrrole-2, 5-diyl)(4-dimethylaminobenzyliene)(3 -acetylpyrrolequinodimethane-2, 5-diyl)] (PAPDMABE) - and its precursor were synthesized by a simple method andcharacterized by ~1H-NMR, FT-IR, TGA and UV-VIS. The polymer can be dissolved in strong polar solvents such as DMSO,DMF or NMP. The band-gap energy of PAPDMABE was found to be 0.95 eV. The conductivity of doped products withiodine falls in the range of a semiconductor.     

Radiation-grafted proton exchange membranes based on co-grafting from binary monomer mixtures into poly(ethylene-co-tetrafluoroethylene) (ETFE) film

In this study, proton exchange membranes (PEMs) based on a poly(ethylene-co-tetrafluoroethylene) (ETFE) film were synthesized through the graft copolymerization of styrene and VTMS (vinyltrimethoxysilane), or styrene and TMSPM (3-(trimethoxysilyl) propyl methacrylate) binary monomer systems using a simultaneous irradiation method. The prepared membranes with the similar degrees of grafting were investigated by measuring ion exchange capacity, proton conductivity, water uptake, chemical stability, and dimensional stability. The results indicate that the silane-crosslinked proton exchange membrane (PEM) has not only lower water uptake and dimensional change but also high proton conductivity at low humidity condition compared to non-crosslinked poly(ethylene-co-tetrafluoroethylene)-g-poly(styrene sulfonic acid) (ETFE-g-PSSA). Also, the chemical stability of silane-crosslinked fuel cell membranes was more improved than that of non-crosslinked fuel cell membrane.     

Sequence dependence of charge transport properties of DNA

The electrical conduction through three short oligomers (26 base pairs, 8 nm long) with differing numbers of GC base pairs was measured. One strand is poly(A)-poly(T), which is entirely devoid of GC base pairs. Of the two additional strands, one contains 8 and the other 14 GC base pairs. The oligomers were adsorbed on a gold substrate on one side and to a gold nanoparticle on the other side. Conducting atomic force microscope was used for obtaining the current versus voltage curves. We found that in all cases the DNA behaves as a wide band-gap semiconductor, with width depending on the number of GC base pairs. As this number increases, the band-gap narrows. For applied voltages exceeding the band-gap, the current density rises dramatically. The rise becomes sharper with increasing number of GC base pairs, reaching more than 1 nA/nm2 for the oligomer containing 14 GC pairs.     

Synthesis, characterization, and transistor response of semiconducting silole polymers with substantial hole mobility and air stability. Experiment and theory

Realizing p-channel semiconducting polymers with good hole mobility, solution processibility, and air stability is an important step forward in the chemical manipulation of charge transport in polymeric solids and in the development of low-cost printed electronics. We report here the synthesis and full characterization of the dithienosilole- and dibenzosilole-based homopolymers, poly(4,4-di-n-hexyldithienosilole) (TS6) and poly(9,9-di-n-octyldibenzosilole) (BS8), and their mono- and bithiophene copolymers, poly(4,4-di-n-hexyldithienosilole-alt-(bi)thiophene) (TS6T1, TS6T2) and poly(9,9-di-n-octyldibenzosilole-alt-(bi)thiophene) (BS8T1, BS8T2), and examine in detail the consequences of introducing dithienosilole and dibenzosilole cores into a thiophene polymer backbone. We demonstrate air-stable thin-film transistors (TFTs) fabricated under ambient conditions having hole mobilities as large as 0.08 cm(2)/V x s, low turn-on voltages, and current on/off ratios > 10(6). Additionally, unencapsulated TFTs fabricated under ambient conditions are air-stable, an important advance over regioregular poly(3-hexylthiophene) (P3HT)-based devices. Density functional theory calculations provide detailed insight into the polymer physicochemical and charge transport characteristics. A direct correlation between the hole injection barrier and both TFT turn-on voltage and TFT polymer hole mobility is identified and discussed, in combination with thin-film morphological characteristics, to explain the observed OTFT performance trends.     

Immobilized polymeric stationary phases using metalized silica supports

Immobilized presynthesized polymers on porous metalized (zirconized or titanized) silica particles as new stationary phases with improved chemical stability for RP-HPLC are reviewed. The preparations using different polymers, such as poly(methyloctylsiloxane), poly(methyltetradecylsiloxane), and poly(butadiene), different immobilization steps (gamma radiation, thermal treatment, and microwave radiation), and the chromatographic performances of these phases for polar, apolar, acidic, and basic compounds are discussed. The stability of some of these stationary phases using alkaline mobile phases is also presented.     

Fluorinated heteroaromatic polyethers for low dielectric constant / high temperature applications

Several series of poly(arylene ether)s with trifluoromethyl substituents were prepared and characterized. These materials are potential candidates for the use as low dielectric constant insulators (intermetal dielectrics, IMD, and interlayer dielectrics, ILD) on microchips. Thermal stability up to 450 °C and a dielectric constant below 3 preferably below 2.5) is required for this application. The thermal stability of the poly(arylene ether)s was increased from 320°C to more than 500 °C by optimization of the structure of the repeating unit. The dielectric constant of one of the most promising structures was determined to be 2.8. In addition, plasma polymerized thin films from hexafluorobenzene, tetrafluorobenzene, perfluorotoluene and perfluorodecaline were prepared and characterized with respect to solubility, dielectric constant, adhesion, and thermal stability.     

Mechanism of high thermal stability of commercial polyesters and polyethers conjugated with bio‐based caffeic acid

In previous report, we discovered that a novel improvement technique to enhance the thermal properties of poly(L ‐lactide)s (PLLAs) by terminal conjugation with 3,4‐diacetoxycinnamic acid (DACA). In this study, we clarified the mechanism of the enhancement of thermal stability by using commercial polyesters and polyethers. The effect of thermal improvement by the terminal conjugation of DACA on poly(DL ‐lactide), poly(ε‐caprolactone), and poly(ethylene glycol) was almost the same as about 100 °C increase. The amount of residual tin catalyst, which enhances the thermal degradation of polyesters, was reduced at undetected level after the terminal conjugation of DACA probably due to the removal of tin during DACA conjugation process. Furthermore, the π‐π stacking interactions of DACA units and the chemical protection of terminal hydroxyl groups, which enhances intramolecular scission, were also important for the high thermal stability. We clarified that the extreme high thermal stability by DACA conjugation was induced by these above mechanisms. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Modification of capillary electrophoresis capillaries by poly(hydroxyethyl methacrylate), poly(diethylene glycol monomethacrylate) and poly(triethylene glycol monomethacrylate)

Modification of capillary electrophoresis (CE) capillaries by poly(hydroxyethyl methacrylate) (poly(HEMA), poly(diethylene glycol monomethacrylate) (poly(DEGMA) and poly(triethylene glycol monomethacrylate) (poly(TEGMA), was studied. Methods based on physical adsorption of the modifier and on its chemical binding were compared on the basis of the electroosmotic flow (EOF) reproducibility, the EOF dependence on the pH, the symmetry of the peak of positively charged tyramine, the stability of the coating and the separation of standard and milk proteins in the modified capillaries. Reproducible coatings were obtained by chemical binding of the polymers to the capillary walls and by coating with a solution of a polymer, as also demonstrated by the atomic force microscopy.