Three diketopyrrolopyrrole (DPP)-quaterthiophene conjugated polymers, pDPP4T-1, pDPP4T-2, and pDPP4T-3, in which the molar ratios of the urea-containing alkyl chains vs branching alkyl chains are 1:30, 1:20, and 1:10, respectively, were prepared and investigated. In comparison with pDPP4T without urea groups in the alkyl side chains and pDPP4T-A, pDPP4T-B, and pDPP4T-C containing both linear and branched alkyl chains, thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 exhibit higher hole mobilities; thin-film mobility increases in the order pDPP4T-1 < pDPP4T-2 < pDPP4T-3, and hole mobility of a thin film of pDPP4T-3 can reach 13.1 cm(2) V(-1) s(-1) after thermal annealing at just 100 °C. The incorporation of urea groups in the alkyl side chains also has an interesting effect on the photovoltaic performances of DPP-quaterthiophene conjugated polymers after blending with PC71BM. Blended thin films of pDPP4T-1:PC71BM, pDPP4T-2:PC71BM, and pDPP4T-3:PC71BM exhibit higher power conversion efficiencies (PCEs) than pDPP4T:PC71BM, pDPP4T-A:PC71BM, pDPP4T-B:PC71BM, and pDPP4T-C:PC71BM. The PCE of pDPP4T-1:PC71BM reaches 6.8%. Thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3 and corresponding thin films with PC71BM were characterized with AFM, GIXRD, and STEM. The results reveal that the lamellar packing order of the alkyl chains is obviously enhanced for thin films of pDPP4T-1, pDPP4T-2, and pDPP4T-3; after thermal annealing, slight inter-chain π-π stacking emerges for pDPP4T-2 and pDPP4T-3. Blends of pDPP4T-1, pDPP4T-2, and pDPP4T-3 with PC71BM show a more pronounced micro-phase separation. These observations suggest that the presence of urea groups may further facilitate the assemblies of these conjugated polymers into nanofibers and ordered aggregation of PC71BM.
Bacterial cellulose (BC) nanofibers represent an emerging class of highly crystalline bionanofibers with high intrinsic mechanical properties. The remarkable nanofibers with oriented structure and strong interfibrillar interactions can realize high-performance materials. In this study, we demonstrated that macrofibers based on aligned BC nanofibers could be prepared by wet spinning and drawing procedures. The relationship between process conditions, structure, and mechanical properties of macrofibers were investigated. The obtained macrofibers exhibited Young's modulus of 16.4 GPa and tensile strength of 248.6 MPa under the optimum process conditions, in which nanofibers displayed a high degree of alignment. Furthermore, we enhanced the interfacial interactions between nanofibers and obtained better mechanical performance by multivalent ion cross-linking. After exchanging the monovalent Na by Fe, the dried macrofiber reached Young's modulus of 22.9 GPa and tensile strength of 357.5 MPa. Particularly, the resulting macrofibers still maintained good mechanical properties with Young's modulus of 15.9 GPa and tensile strength of 262.2 MPa in the wet condition. This research provided a good method to fabricate macrofibers from BC nanofibers with good properties by continuous wet-spinning process. These macrofibers can be easily functionalized and have promising potential applications in smart textiles, biosensor, and structural reinforcement.
The synthesis and optical investigations of di(p‐methoxylphenyl)dibenzofulvene (1) and its analogues 2, 3, 4, 5, 6, and 7 with different lengths of alkoxyl chains are presented. All of these molecules exhibit emission in the solid state. The following interesting properties are reported for compound 1: 1) the solid‐state fluorescence of 1 is dependent on the polymorphism forms; the two crystalline forms 1a and 1b are strongly blue‐ and yellow‐green‐emissive, whereas the amorphous solid is weakly fluorescent with orange emission; 2) on the basis of crystal‐structural analysis, the intermolecular interactions will restrict the internal rotations, leading to fluorescence enhancement for the two crystalline forms 1a and 1b; however, the difference in emission color between 1a and 1b is ascribed to the molecular conformational alteration; 3) the solid‐state fluorescence of 1 can be tuned by heating and cooling as well as grinding. Importantly, microrods of 1a and 1b exhibit outstanding optical waveguide behaviors. Moreover, amplified spontaneous emission for 1b and multimode‐lasing behavior for 1a are presented. Besides the studies of compound 1, the crystal structures and solid‐state fluorescence behaviors of 2, 3, 4, 5, 6, and 7 are also described.
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