MOLECULAR AND SUPRAMOLECULAR ORDERING IN CONFINED ENVIRONMENTS

Crystal and phase morphologies and structures determined by self-organization of crystalline-amorphous diblockcopolymers, crystallization of the crystallizable blocks, and vitrification of the amorphous blocks are reviewed through asystematic study on a series of poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers. On the base ofcompetitions among these three processes, molecular and supramolecular ordering in confined environments can beinvestigated. In a concentration-fluctuation-induced disordered (D_(CF)) diblock copolymer, the competition between crystalli-zation of the PEO blocks and vitrification of the PS blocks is momtored by time-resolved simultaneous small angle X-rayscattering (SAXS) and wide angle X-ray diffraction (WAXD) techniques. In the case of T_c<T_g^(PS-rich), the crystallization of thePEO blocks is observed to be confined within the bicontinuous D_(CF) phase due to the rapid vitrification of the PS-rich phase.Overall crystallization rate, crystal melting behavior, and crystallinity results further confirm the competition betweencrystallization and vitrification at different temperatures. In an ordered lamellar PEO-b-PS diblock copolymer, the crystalli-zation of the PEO blocks is completely confined within the ordered lamellae due to rapid vitrification of the PS layers asobserved by time-resolved SAXS and WAXD experiments. From the combined two-dimensional SAXS and WAXDmeasurements, the crystal orientation within the confined lamellar geometry is found parallel to the lamellar surface normalwhen it is isothermally crystallized at 35℃. In an ordered cylindrical PEO-b-PS sample, the crystallization of the PEO blocksis also observed to be confined within the ordered cylinders because of rapid vitrification of the PS matrix. The crystalorientation within the confined cylinders is found perpendicular to the cylinder axis as it is crystallized at 35℃.

Characterization of A-and B-type starch granules in Chinese wheat cultivars

Starch is the major component of wheat flour and serves as a multifunctional ingredient in food industry. The objective of the present study was to investigate starch granule size distribution of Chinese wheat cultivars, and to compare structure and functionality of starches in four leading cultivars Zhongmai 175, CA12092, Lunxuan 987, and Zhongyou 206. A wide variation in volume percentages of A- and B-type starch granules among genotypes was observed. Volume percentages of A- and B-type granules had ranges of 68.4–88.9% and 9.7–27.9% in the first cropping seasons, 74.1–90.1% and 7.2–25.3% in the second. Wheat cultivars with higher volume percentages of A- and B-type granules could serve as parents in breeding program for selecting high and low amylose wheat cultivars, respectively. In comparison with the B-type starch granules, the A-type granules starch showed difference in three aspects：（1） higher amount of ordered short-range structure and a lower relative crystallinity,（2） higher gelatinization onset（To） temperatures and enthalpies（ΔH）, and lower gelatinization conclusion temperatures（Tc）,（3） greater peak, though, and final viscosity, and lower breakdown viscosity and pasting temperature. It provides important information for breeders to develop potentially useful cultivars with particular functional properties of their starches suited to specific applications.

Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides

Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants（k） were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity,all of the investigated organic compounds were divided into two groups（Group A and Group B）. The percentage adsorption of organic compounds in Group A was less than 15%（wt./wt.）and that in the Group B was higher than 15%（wt./wt.）. For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation（as a synergistic process） took place. Results showed that the relationship between the rate constants（k values） and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process,EHOMOand Fukui indices（f（0）_x, f（-）_x, f（＋）_x） were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process.

High performance organic transistors and phototransistors based on diketopyrrolopyrrole-quaterthiophene copolymer thin films fabricated via low-concentration solution processing

Conjugated polymers have received considerable attentions over the past years due to their large-area potential applications via low-cost solution processing. Improving crystallinity of conjugated polymer molecules in solution-processed thin films is crucial for their efficient charge transport and thus high performance optoelectronic devices. Herein, with diketopyrrolopyrrole-quaterthiophene （PDQT） copo/ymer as an example, it is found that by simply reducing the solution concentration for spincoating meanwhile with the assistance of post-annealing, significantly enhanced film crystallinity with formation of typical single crystalline domains is obtained, which benefits from the enough space for better molecular assembly especially at the semiconductor/dielectric interface. High performance polymer transistors and phototransistors were finally constructed based on the optimal lowconcentration （2 mg/mL） spin-coated PDQT films （～12 nm）, which giving a high charge carrier mobility of 2.28 cm2 V-1 s-1 and a photoresponse on/off ratio of 2.1 ×107 at VG = 0 V under white light irradiation of 6mW/cm2. The results suggest that the bright future of PDQT crystalline films for large-area flexible integrated optoelectronic devices and the application of effective low-concentration processing approach in solution-processed organic electronics with reduced material waste.