Mesogenic and optical properties of α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes

Liquid crystalline α,α′‐bis(4‐alkoxyphenylethynyl)oligothiophenes (bi‐ and ter‐thiophene) have been synthesized and their mesogenic behaviour and optical properties investigated. They all exhibited a nematic mesophase, and compounds with long alkoxy chains also showed lamellar phases. Increasing the number of thiophene units increased both the transition temperatures and the mesophase ranges. As for their optical properties, incorporating more thiophene units results in red‐shifted absorption and emission spectra, slightly enhanced quantum efficiency, and a larger Stoke's shift. Most importantly, in terms of the absorption and emission maxima, the incorporation of one 4‐alkoxyphenylethynyl moiety was found to be equivalent to adding one thiophene ring.     

Ranking Oxidant Sensitiveness: A Guide for Synthetic Utility

Common oxidants used in chemical synthesis, including newly developed perruthenates, were evaluated in the context of understanding (and better appreciating) the sensitiveness and associated potential hazards of these reagents. Analysis using sealed cell differential scanning calorimetry (scDSC) facilitated Yoshida correlations, which were compared to impact sensitiveness and electrostatic discharge experiments (ESD), that enabled sensitiveness ranking. Methyltriphenylphoshonium perruthenate (MTP3, 8 ), isoamyltriphenylphosphonium perruthenate (ATP3, 7 ) and tetraphenylphosphonium perruthenate (TP3, 9 ) were found to be the most sensitive followed by 2-iodoxybenzoic acid (IBX, 2 ) and benzoyl peroxide (BPO, 10 ), whereas the most benign were observed to be Oxone ( 12 ), manganese dioxide (MnO₂, 13 ), and N-bromosuccinimide (NBS, 17 ).     

Flash DSC crystallization study for blown film grade bimodal HDPE resins. I. Isothermal kinetics and its application of the blown film modeling

Isothermal ultra‐cooling crystallization tests were conducted on three blown film grade bimodal HDPE resins using an ultrafast scanning calorimeter, the Flash DSC. Isothermal tests were performed to study the regime transition, the thermal nucleation and the spherulitical growth using the Hoffman‐Lauritzen theory in a range between 90 °C and 116 °C. Temperature profile estimations using such data were in good agreement with actual blown film process data. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2425–2431     

A different approach for determining the responsivity of n~+p detectors using scanning electron microscopy

正This paper explores an alternative to the standard method of studying the responsivities(the input-output gain) and other behaviours of detectors at low electron energy.The research does not aim to compare the results of differently doped n~+p detectors;its purpose is to provide an alternative characterization method(using scanning electron microscopy) to those used in previous studies on the responsivity of n~+p doped detectors as a function of the electron radiation energy and other interface parameters.     

Siloxane polymers containing azo moieties synthesized by click chemistry for photo responsive and liquid crystalline applications

Three new types of siloxane‐based photoactive liquid crystalline polymers containing azo side groups were synthesized through the click chemistry route. The polymers having molecular weight range of 14,000–34,000 g mol^?1 were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and dichloromethane. The photoresponsive trans–cis photoisomerization under UV radiation and cis–trans relaxation process in dark for the polymers were studied. The isomerization rate constants were found to be 0.01–0.04 sec^?1 and 1.16*10^?4–4.67*10^?4 sec^?1, respectively. It has been noted that the polymers showed high intensity absorption for n‐π* in chloroform. Both trans and cis forms of azide monomers having azo moiety exhibited molar extinction coefficient ( ? _max) in the range of 22,000–33,000 L mol^?1 cm^?1. The thermotropic behavior of the polymers was studied by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) experiments. Polymer P1 showed liquid crystalline textures of nematic droplets, whereas P2 showed smectic focal conic texture and nematic droplets. Polymer P1 was also studied for photomechanical bending on exposure to UV radiation. The polymers showed initial degradation temperature in the range of 210–275°C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Click chemistry‐based synthesis of azo polymers for second‐order nonlinear optics

Four linear polymers containing pendant azo moiety were synthesized through click chemistry for second‐order nonlinear optical study. The polymers were found soluble in most of the polar organic solvents such as tetrahydrofuran (THF), chloroform, and dimethyl formamide (DMF). The polymers showed thermal stability up to 300 °C and glass transition temperatures (T_g) in the range of 120–140 °C. The molecular weights (M_w) of these polymers (measured by gel permeation chromatography) were in the range 37,900–55,000 g/mol. The polymers were found to form optically transparent films by solution casting from THF solution. Order parameters were calculated from UV–vis absorption spectra. The morphology changes in the films after poling were characterized by atomic force microscopy. The angular dependence, temperature dependence, and time dependence of second harmonic generation (SHG) intensity were obtained by using 1064 nm Nd:YAG laser. The SHG intensity remained unchanged up to 95 °C. At room temperature, it remained stable up to 8 days after initial drop of about 14%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Bio‐based comb‐like copolymers derived from alkyl 10‐undecenoates and maleic anhydride

In this article, 10‐undecenoic acid, based on castor oil, was used a raw material for the synthesis of alternating copolymers. ω‐Unsaturated fatty esters as alkyl 10‐undecenoates were prepared by the esterification reaction of 10‐undecenoic acid with alkyl alcohol. A series of comb‐like copolymers were synthesized by free radical polymerization from maleic anhydride and alkyl 10‐undecenoates copolymers with different length of alkyl side chains in a toluene solution. These copolymers were investigated by ¹H and ¹³C nuclear magnetic resonance, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry (DSC). The copolymers were obtained in a low molecular weight in a range 3370–12,240 g mol⁻¹ and their structural characterization indicated the formation of alternating copolymers. DSC characterization revealed that these comb‐like copolymers showed amorphous to semicrystalline behavior by increasing the length of side chains. The bio‐based comb‐like copolymers allow for the development of new polymeric materials for several applications. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1039–1045