Recent Advances in Lignocellulose-Based Monomers and Their Polymerization.

Replacing fossil-based polymers with renewable bio-based polymers is one of the most promising ways to solve the environmental issues and climate change we human beings are facing. The production of new lignocellulose-based polymers involves five steps, including (1) fractionation of lignocellulose into cellulose, hemicellulose, and lignin; (2) depolymerization of the fractionated cellulose, hemicellulose, and lignin into carbohydrates and aromatic compounds; (3) catalytic or thermal conversion of the depolymerized carbohydrates and aromatic compounds to platform chemicals; (4) further conversion of the platform chemicals to the desired bio-based monomers; (5) polymerization of the above monomers to bio-based polymers by suitable polymerization methods. This review article will focus on the progress of bio-based monomers derived from lignocellulose, in particular the preparation of bio-based monomers from 5-hydroxymethylfurfural (5-HMF) and vanillin, and their polymerization methods. The latest research progress and application scenarios of related bio-based polymeric materials will be also discussed, as well as future trends in bio-based polymers.

[Hyoid body morphology of thyroglossal duct cyst: a comparative study based on imaging].

Objective:To provide reference for preoperative diagnosis and treatment of thyroglossal duct cyst by studying the morphological changes of hyoid body. Methods:The CT data（midsagittal image） of congenital thyroglossal duct cyst（TGDC group） diagnosed by pathology and the control group（C group） were collected from January 2016 to October 2021. The differences of hyoid body height（HBH）, hyoid body width（HBW）, hyoid bone thickness（HBT）, HBW/HBH, HBT/HBH between the two groups were compared. HBH, HBW and HBT were analyzed by t-test; The HBW/HBH and HBT/HBH were analyzed by Mann-Whitney U test. Results:Twenty-nine cases were included in the TGDC group and 58 in the C group. The HBH in the TGDC group was（8.93 ±0.22） mm and that in the C group was（8.94±0.12） mm, there was no significant difference between the two groups（P>0.05）. The HBW in the TGDC group and the C group were（5.09±0.21） mm and（4.48±0.11） mm, and the HBT were（3.84±0.12） mm and（3.13±0.08） mm, respectively, the difference between the two groups was statistically significant（P<0.05）. The average rank sum of HBW/HBH in the TGDC group and the C group was 53.95 and 39.03, respectively, and the average rank sum of HBT/HBH was 59.90 and 36.05, respectively, the difference between the two groups was statistically significant（P<0.05）. Conclusion:The morphological changes of hyoid body of thyroglossal duct cyst may be helpful for preoperative diagnosis, and it also suggests that hyoid body resection may reduce the possibility of postoperative recurrence.

Interfacial Nanostructuring of Poly(vinylidene fluoride) Homopolymer with Predominant Ferroelectric Phases.

Facile preparation of poly(vinylidene fluoride) (PVDF) homopolymer nanoparticles (NPs) with monodispersed size distribution and predominant ferroelectric phases was done in an interfacial nonsolvent (water/methanol)-solvent (dimethylformamide (DMF))-polymer (PVDF) ternary system using two interfacial nanoassembly methods. First, a fluidic liquid-liquid interface consisting of two miscible solvents was created by introducing nonsolvent (water) under the PVDF solution. After the interface was created, the interface moved up to the DMF phase direction; PVDF NPs were produced through nonsolvent-induced phase separation. As the water content decreased in the nonsolvent by mixing with methanol, PVDF structures changed from nanoparticles with 252 nm average diameter (PVDF NP-1) to a porous membrane through membrane-wrapped NPs. The phenomena were found to be related to the mutual affinity of solvent, nonsolvent, and PVDF. When an additional external force was introduced to the water-DMF-PVDF system through magnetic stirring (reprecipitation method), smaller PVDF NPs with 61.4 nm diameter were obtained (PVDF NP-2). Both the as-prepared PVDF NPs were demonstrated with the predominant ferroelectric (electroactive (EA)) phase up to 97-98% among crystalline phases, which is apparently the highest value ever reported for PVDF homopolymer NPs. It is noteworthy that PVDF NP-2 showed a higher ß phase ratio than that of PVDF NP-1, as proved using Fourier transform infrared (FT-IR) spectroscopy. Also, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements revealed that PVDF NP-1 exhibited higher crystallinity and that PVDF NP-2 underwent a well-separated two-step phase transition under heating. Results suggest that controlling interface formation with DMF and water plays a crucial role in manipulating ferroelectric PVDF nanostructures in terms of crystallinity and the ferroelectric ß phase-to-γ phase ratio.

Cellulose Nanofiber Nanosheet Multilayers by the Langmuir-Blodgett Technique.

We describe a systematic approach for producing cellulose nanofiber (CNF) nanosheets using the Langmuir-Blodgett (LB) technique. The CNFs were obtained from sulfuric acid hydrolysis of commercially available microfibrillated cellulose. Needle-like CNFs, negatively charged by grafted sulfate groups, were maintained at the air-water interface, assisted by amphiphilic polymer, poly( N-dodecyl acrylamide) (pDDA). The CNFs produced a stable monolayer. The surface pressure increased steadily with a high collapse pressure of 50 mN m-1 when spread with formic acid and pDDA. The composite monolayers were transferred onto solid substrates as Y-type LB films using a vertical dipping method. Upstroke and downstroke transfer ratios of the films were, respectively, unity and 0.88, indicating that full coverage was achieved by the monolayer even for more than 200 layers. Results obtained using atomic force microscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy showed that CNF nanosheets possess well-defined layer structures with average monolayer thickness of 5.3 nm. The relative amount of CNFs in the nanosheets was calculated as 62.6 wt % using the quartz crystal microbalance technique. The as-prepared nanosheets are optically transparent to visible light and have high hydrophobicity. In fact, the nanosheet transparency was higher than 88% at 600 nm wavelength for 24 layers. A miniscule amount of pDDA enables demonstration of free-standing CNF nanosheets with 1 cm width and 45.6 nm thickness (23 layers).

Resistive non-volatile memories fabricated with poly(vinylidene fluoride)/poly(thiophene) blend nanosheets.

Ferroelectric poly(vinylidene fluoride)/semiconductive polythiophene (P3CPenT) blend monolayers were developed at varying blend ratios using the Langmuir-Blodgett technique. The multilayered blend nanosheets show much improved surface roughness that is more applicable for electronics applications than spin-cast films. Because of the precisely controllable bottom-up construction, semiconductive P3CPenT were well dispersed into the ferroelectric PVDF matrix. Moreover, the ferroelectric matrix contains almost 100% ß crystals: a polar crystal phase responsible for the ferroelectricity of PVDF. Both the good dispersion of semiconductive P3CPenT and the outstanding ferroelectricity of the PVDF matrix in the blend nanosheets guaranteed the success of ferroelectric organic non-volatile memories based on ferroelectricity-manipulated resistive switching with a fresh high ON/OFF ratio and long endurance to 30 days.

Regioselective Synthesis of Eight-Armed Cyclosiloxane Amphiphile for Functional 2D and 3D Assembly Motifs.

A crystalline tetramethylcyclotetrasiloxane (TMCS)-derived amphiphile was regioselectively synthesized with eight peripheral hydrophilic amide groups and hydrophobic dodecyl chains by Pt(0)-catalyzed hydrosilylation and amidation reactions. The as-synthesized materials showed ordered lamellar structure formation in the powder form. It also exhibits superior two-dimensional (2D) monolayer formation properties at the air-water interface with unexpectedly high collapse surface pressure and elastic modulus. The monolayers act as two-dimensional building blocks with finely controllable thickness on a several nanometer scale irrespective of the substrate type and properties. The amphiphile forms nanofibers spontaneously by good-poor solvent strategies, which contributes to porous three-dimensional (3D) structures possessing superhydrophobic surface wettability.

Solvent-dependent properties of poly(vinylidene fluoride) monolayers at the air-water interface.

The present work addresses the solvent-dependent properties of Langmuir films of poly(vinylidene fluoride) (PVDF) and amphiphilic poly(N-dodecylacrylamide) (pDDA) at different mixing ratios. After introducing pDDA nanosheets, PVDF Langmuir films obtain a tremendously enhanced modulus as well as high transfer ratios using the vertical dipping method caused by the support of the pDDA two-dimensional hydrogen bonding network. Brewster angle microscopy (BAM) was used to investigate PVDF monolayers at the air-water interface in situ. Spreading from different solvents, the PVDF molecules take completely different aggregation states at the air-water interface. The PVDF molecules aggregate to become large domains when spread from N-methyl-2-pyrrolidone (NMP). However, the volatile and low-polarity methylethyl ketone (MEK) made the PVDF molecules more dispersive on the water surface. This study also discovers a versatile crystallization control of PVDF homopolymer from complete ß phase (NMP) to complete α phase (MEK) at the air-water interface, thereby eliciting useful information for further manipulation of film morphologies and film applications.