Synthesis and Liquid Crystalline Behavior of Side Chain Liquid Crystalline Polymers Containing Triphenylene Discotic Mesogens with Different Length Flexible Spacers

A series of side chain liquid crystalline polymers （SCLCPs） containing triphenylene （Tp） units in the side chains, denoted as PMTS （without spacer） and PMTnS （n = 2, 3, 4, 6, which is the number of the methylene units between the main chain and Tp moieties in the side chains）, with different lengths of spacers were synthesized through conventional free radical polymerization. The chemical structures of the monomers were confirmed by 1H/IaC-NMR, and the phase behaviors were examined by differential scanning calorimetry （DSC）, polarized optical microscopy （POM） and wide-angle X-ray diffraction （1D and 2D WAXD）. The molecular characterization of the polymers was performed with 1H-NMR, gel permeation chromatography （GPC） and thermogravimetric analysis （TGA）. The phase behaviors of the polymers have been investigated by a combination of techniques including DSC, POM, 1D and 2D WAXD. The results showed that the length of spacer has significant effects on the LC phase behavior of polymers. For PMTS and PMT2S, they displayed the columnar phase developed by the Tp moieties and the main chain as a whole due to the strong coupling effect of the Tp moieties and the main chain. For the PMT3S, PMT4S and PMT6S, they formed the symmetry hexagonal columnar （~n） phase owing to the decoupling effect. All of these indicated that the ＂decoupling effect＂ or ＂coupling effect＂ depended on the length of spacers, leading to the different LC phase formation mechanism.

Synthesis,Characterization and Phase Behaviors of Polypeptides Bearing Biphenyl Mesogens and Oligo-Ethylene-Glycol Tails

A series ofpolypeptides bearing biphenyl mesogenic side-chains and oligo-ethylene-glycol （OEG） tails （PPLGn-g- BPOEGm, n = 26 and 63, m = 2, 3, and 7） has been synthesized via a 1,3-dipolar cycloaddition with quantitative grafting density. FTIR results revealed that the polypeptides adopted highly stable a-helix in the temperature range of 25-200 ℃. DSC, POM and WAXS analysis revealed that PPLGn-g-BPOEGm （m ≤ 3） samples with short OEG tail length showed two main phase transitions including crystal to liquid crystalline （smectie C, SmC） phase transition and the melting transition of crystalline E-phase, while PPLG,-g-BPOEG7 with longer OEG tail length （m = 7） exhibited the melting transitions without the formation of liquid crystalline phase.

Editing the Shape Morphing of Monocomponent Natural Polysaccharide Hydrogel Films

Shape-morphing hydrogels can be widely used to develop artificial muscles,reconfigurable biodevices,and soft robotics.However,conventional approaches for developing shape-morphing hydrogels highly rely on composite materials or complex manufacturing techniques,which limit their practical applications.Herein,we develop an unprecedented strategy to edit the shape morphing of monocomponent natural polysaccharide hydrogel films via integrating gradient cross-linking density and geometry effect.Owing to the synergistic effect,the shape morphing of chitosan(CS)hydrogel films with gradient cross-linking density can be facilely edited by changing their geometries(length-to-width ratios or thicknesses).Therefore,helix,short-side rolling,and longside rolling can be easily customized.Furthermore,various complex artificial 3D deformations such as artificial claw,horn,and flower can also be obtained by combining various flat CS hydrogel films with different geometries into one system,which can further demonstrate various shape transformations as triggered by pH.This work offers a simple strategy to construct a monocomponent hydrogel with geometry-directing programmable deformations,which provides universal insights into the design of shape-morphing polymers and will promote their applications in biodevices and soft robotics.

Multiple Effects Tailoring the Self-organization Behaviors of Triphenylene Side-chain Liquid Crystalline Polymers via Changing the Spacer Length

Long-alkyl tail triphenylene （TP） side-chain liquid crystalline polymers （SCLCPs） with different spacer length （P-m-TP, m = 2, 3, 4, 6, 8, which is the number of carbon atom in the flexible alkyl spacers） have been successfully synthesized via free radical polymerization. The differential scanning calorimetry （DSC）, polarized light microscopy （POM）, ultraviolet-visible spectroscopy （UV- Vis）, wide-angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） measurements were performed to investigate the influence of multiple effects on the self-organization behaviors of P-m-TP, including steric effect, decoupling effect and π-π stacking effect. The experimental results revealed that P-m-TP （m = 2, 3, 4） formed the columnar phase which was developed by the TP moieties and the main chain as a whole, suggesting that the side-chains had strong steric effect even though the number of spacer length （m） exceeded 4. In addition, the clearing points （Tis） of the polymers were above 300 ℃. When m = 6 and 8, the polymers displayed hexagonal columnar phase and exhibited the low Tis （91 and 80 ℃ respectively）, originating from the self-assembly of triphenylene due to the decoupling effect and π-π stacking effect. This work offers a viable and inspiring pathway to control the phase transition temperature and phase structure ofTP SCLCPs via simply tailoring the spacer length and increasing the alkyl tail length of TP.

A universal strategy for achieving dual cross-linked networks to obtain ultralong polymeric room temperature phosphorescence

Efficient polymeric room-temperature phosphorescence(PRTP)with excellent processability and flexibility is highly desirable but still faces formidable challenge.Herein,a general strategy is developed for efficient PRTP through photo-polymerization of phosphor monomers and N-isopropylacrylamide(NIPAM)spontaneously without a crosslinker.Remarkably ultralong lifetime of 3.54 s with afterglow duration time of 25 s and decent phosphorescent quantum efficiency of 13%are achieved.This efficient PRTP has been demonstrated to be derived from the synergistic effect of the covalent and hydrogen bonds networks formed through photo-polymerization of NIPAM.The electron paramagnetic resonance(EPR)spectra confirmed that methyl radicals are generated under the irradiation of ultraviolet light and promote the formation of covalent cross-linking networks.This strategy has also been proved to be generalizable to several other phosphor monomers.Interestingly,the polymer films display ultrahigh temperature resistance with long afterglows even at 140℃ and unexampled ultralong lifetime of 2.45 s in aqueous solutions.This work provides a simple and feasible avenue to obtain efficient PRTP.