Transformation of Corn Stover into Furan Aldehydes by One-Pot Reaction with Acidic Lithium Bromide Solution.

Currently, the production of furan aldehydes from raw biomass suffers from low furfural yield and high energy consumption. In this study, a recyclable and practical method was explored for the preparation of furfural from corn stover by the one-pot reaction by acidic lithium bromide solution (ALBS) without pretreatment and enzymolysis. In the ALBS reaction, the furan aldehydes were generated by the degradation of lignocellulose; however, the products were unstable and were further dehydrated to form humins. So, dehydration reaction was inhibited in this study, and the high yield of furan aldehydes was obtained, in which 2.94 g/L of furfural and 2.78 g/L of 5-hydroxymethyl furfural (5-HMF) were generated with high solid loading (10 wt%), the presence of commercial catalyst ZSM-5 and co-solvent tetrahydrofuran (THF) at 140 °C for 200 min. Via this method, almost 100% of hemicellulose was transformed to furfural, and 40.71% of cellulose was transformed to 5-HMF, which was based on the theoretical yield of HMF (8.35 g) from glucose (29.30 g) produced from cellulose. After the reaction, the catalyst ZSM-5 was the main component in the solid residue and kept a suitable performance. THF azeotrope was easily separated from the slurry by evaporation. During the removal of THF, lignin was precipitated from the liquid phase and showed lower molecular weight and abundant active groups, which was a potential feedstock for producing valuable aromatics and polymers. Thus, in a one-pot reaction, the ideal yield of furan aldehydes from raw biomass was obtained on a lab scale, and the catalyst, THF, and LiBr were easily recycled, which provided an option to realize the economical production of sustainable furan aldehydes from raw biomass.

Synthesis of Metallopolymers and Direct Visualization of the Single Polymer Chain.

During the past few decades, the study of the single polymer chain has attracted considerable attention with the goal of exploring the structure-property relationship of polymers. It still, however, remains challenging due to the variability and low atomic resolution of the amorphous single polymer chain. Here, we demonstrated a new strategy to visualize the single metallopolymer chain with a hexameric or trimeric supramolecule as a repeat unit, in which Ru(II) with strong coordination and Fe(II) with weak coordination were combined together in a stepwise manner. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM) and scanning tunneling spectroscopy (STS), we were able to directly visualize both Ru(II) and Fe(II), which act as staining reagents on the repeat units, thus providing detailed structural information for the single polymer chain. As such, the direct visualization of the single random polymer chain is realized to enhance the characterization of polymers at the single-molecule level.

Lignin-xylan nanospheres prepared by green and quick method from lignocellulose and used as additive in PVA films.

Lignin, as an amorphous three-dimensional aromatic polymer, was able to self-assemble into lignin nanoparticles (LNPs) to realize valorization of lignin. Here, lignin-xylan extractives were extracted from grape seed (GS) and poplar by acidic THF at room temperature, and effectively produced lignin-xylan nanospheres via spin evaporation. The morphology and chemical properties of nanospheres were determined by its natural origins, consequently influencing its application. For the lignin-xylan extractive from grape seed, the lignin was composed of guaiacyl (G) and p-hydroxylphenyl (H) units and the hollowed nanospheres (GS-LNPs) with 362.72 nm diameter was produced. The extractive from poplar was composed of G-syringyl (S) typed lignin (80.30 %) and xylan (12.33 %), that can assemble into LNPs with smaller size (229.87 nm), better PDI (0.1), and light color. The hybrid particles showed the qualities of lignin and xylan, that properties led to the LNPs@PVA composite films with UV-blocking capability, strong mechanical strength and hydrophobicity, and transparency ability of visible light. P-LNPs showed better performance as the film additives, due to its lower particles size and high content of unconjugated -OH from xylan. Xylan was significant in the composite films, and lowering the xylan content resulted in the decrease of the composite film's mechanical properties and hydrophobicity.

The role of glycosylation in non-productive adsorption of cellulase to lignin isolated from pretreated corn stover.

Glycosylation, a general post-translational modification for fungal cellulase, has been shown to affect cellulase binding to its substrate. However, the exact impact of glycosylation on cellulase-lignin interaction remain unclear. Here, we demonstrated that the lignin isolated from tetrahydrofuran-pretreated corn stover exhibits strong adsorption capability to cellulase due to its negatively charged and porous structure. For the cellulases with varying glycosylation levels, the less-glycosylated protein showed high adsorption capability to lignin, and that trend was observed for the main cellulase components secreted by Penicillium oxilicum, including endoglucanase PoCel5B, cellobiohydrolase PoCel7A-2, and ß-glucosidase PoBgl1. Additionally, N-glycan sites and motifs were examined using mass spectrometry, and protein structures with N-glycans were constructed, where PoBgl1 and PoCel7A-2 contained 13 and 1 glycosylated sites respectively. The results of molecular dynamics simulations indicated that the N-glycans impacted on the solvent-accessible surface area and secondary structure of protein, and the binding conformation of lignin fragment on cellulase, resulting in a decrease in binding energy (14 kcal/mol for PoBgl1 and 13 kcal/mol for PoCel7A-2), particularly for van der Waals and electrostatic interaction. Those findings suggested that glycosylation negatively impacted the lignin-cellulase interaction, providing a theoretical basis for the rational engineering of enzymes to reduce lignin-enzyme interaction.

Polyvinyl alcohol/phytic acid/phosphorylated chitosan hydrogel electrode highly efficient electroadsorption of low concentration uranium from uranium tailings leachate.

In order to improve the removal rate of uranium and reduce the harm of radioactive pollution, a physically crosslinked polyvinyl alcohol/phosphorylated chitosan (PPP) hydrogel electrode was designed by freezing thawing method. The results show that PPP hydrogel has a good adsorption effect on uranium, and 200 mL of uranium tailings leachate is absorbed, and the treatment efficiency reaches 100 % within 15 min. PPP hydrogel can adapt to a wide range of pH conditions and exhibit excellent adsorption efficiency in the range of 3-9. At the same time, PPP hydrogel maintains an adsorption efficiency of over 85 % for 950 mg/L uranium solution. This lays the foundation for the practical application of PPP hydrogel. In addition, PPP hydrogel also exhibits good repeatability, after 7 cycles, the material still retains 95 % of its initial performance. The synergistic effect of various functional groups such as phosphate, hydroxyl, and ammonium in the material is the main mechanism of PPP's adsorption capacity for uranium. Furthermore, electrochemical adsorption method significantly enhances the adsorption performance of PPP hydrogel.

Preparation of novel polyvinyl alcohol-carbon nanotubes containing imidazolyl ionic liquid/chitosan hydrogel for highly efficient uranium extraction from seawater.

A novel polyvinyl alcohol-carbon nanotube containing an imidazolyl ionic liquid/chitosan composite hydrogel (termed CBCS) was prepared for highly selective uranium adsorption from seawater. The results show that CBCS has good adsorption properties for uranium within the pH range of 5.0-8.0. Kinetics and thermodynamics experiments show that the theoretical maximum adsorption capacity of CBCS to U(VI) is 496.049 mg/g (288 K, pH = 6.0), indicating a spontaneous exothermic reaction. Mechanism analysis shows that the hydroxyl group, amino group, and CN bond on the surface of CBCS directly participate in uranium adsorption and that the dense pores on the surface of CBCS play an important role in uranium adsorption. The competitive adsorption experiment shows that CBCS has excellent uranium adsorption selectivity. In addition, CBCS exhibits good reusability. After five adsorption-desorption cycles, the uranium adsorption rate of CBCS can still reach >98 %. Hence, CBCS has excellent potential for uranium extraction from seawater.

Selective, rapid extraction of uranium from aqueous solution by porous chitosan-phosphorylated chitosan-amidoxime macroporous resin composite and differential charge calculation.

Herein, a new porous chitosan-phosphorylated chitosan-amidoxime macroporous resin composite (PCAR) was designed and synthesized for the rapid and selective extraction of uranium resources from aqueous solution. This study showed that PCAR exhibited excellent adsorption toward uranium in a pH range of 5-9. The dynamic adsorption process aligned with the quasi-second-order kinetic model and corresponded to the chemical adsorption process. The maximum adsorption capacity was 561.28 mg·g-1 at pH 6 and 308 K. Mechanism analysis showed that the synergistic effect of the amidoxime group (-(NH2)C=N-OH), PO, and -NH2 on the PCAR surface improved the uranium adsorption performance. The differential charge density indicated that the amidoxime and phosphate groups provide lone-pair electrons for the adsorption of UO22+ and their synergistic effect improves the UO22+ adsorption performance of PCAR. The uranium distribution coefficients of PCAR and CAR are 4.6 and 2.4 times those of vanadium, respectively. These results indicate that phosphorylation can ameliorate the disadvantage of competitive vanadium adsorption of the amidoxime adsorbent. In addition, PCAR exhibits good reusability and stable adsorption capacity after five adsorption-desorption cycles. Hence, PCAR has excellent potential for uranium extraction from aqueous solution.

A quantitative study of nanoplastics within cells using magnetic resonance imaging.

Concerns regarding the environmental hazards and health risks of nanoplastics (NPs) are increasing. However, quantifying of NPs in vivo remains challenging. In this study, we propose a strategy for using magnetic resonance imaging (MRI) to quantify NPs internalized by mouse macrophages. Model NPs (Fe3O4@PS) with more homogeneous sizes and morphologies were obtained by encapsulating Fe3O4 in polystyrene. A standard curve was generated by linearly fitting the intensity and concentration charts to the Fe3O4@PS MRI data. The mass of Fe3O4@PS captured by the mouse macrophages was estimated using a standard curve. An explanation of how the standard curves were created and used is provided in the text. The accuracy of the MRI results was demonstrated using, inductively coupled plasma (ICP). Quantitative results from MRI and ICP revealed that the mouse macrophage uptake increased as NPs concentrations decreased. According to the ICP results, when the NPs exposure concentration was 10 µg/mL, the uptake rate by mouse macrophages was 63.0 %. The quantitative MRI results were slightly lower than those for ICP, with an uptake rate of 57.7 % in mouse macrophages at the same concentration. Therefore, MRI provides a new perspective for quantitative NPs analysis.

Solid lipid nanoparticles for phytosterols delivery: The acyl chain number of the glyceride matrix affects the arrangement, stability, and release.

The lipid matrix plays a key role in solid lipid nanoparticles (SLNs) embedding active ingredients. To investigate the influence of lipid matrix structure on arrangement, release, and stability of solid lipid nanoparticles, three phytosterols formulations with different carrier glycerides [glycerol monostearate (GMS), glycerol distearate (GDS), and glycerol tristearate (GTS)] were prepared and evaluated. X-ray diffraction and differential scanning calorimetry revealed the lowest crystallinity of phytosterols in the GMS matrix, corresponding to the maximum bioaccessibility (40.2%) in vitro experiments. Sustained release and better stability were observed from GDS and GTS matrices, which could be attributed to strong molecular interactions or a core-rich structure inside the nanoparticles. Molecular dynamics simulations demonstrated that the affinity between phytosterols and glycerides decreased in the order GDS > GTS > GMS, as well as explaining the release and storage capacities of the three nanoparticles. This study would facilitate the rational design of SLNs in functional foods.

Orthodontic retreatment of an adult woman with mandibular backward positioning and temporomandibular joint disorder: A case report.

BACKGROUND: The role of occlusal factors on the occurrence of temporomandibular joint disorders (TMDs) is still unclear and it is tricky for orthodontists to treat malocclusions in patients with TMDs. We report the case of the second orthodontic treatment of an adult female with Class II division 2 malocclusion associated with TMD. With the removal of anterior occlusal interference, TMD symptoms were alleviated and cone beam computed tomography (CBCT) images showed the bilateral condyles shifted forward. CASE SUMMARY: This case report presented an orthodontic retreatment of an adult female with TMD and mandibular backward positioning based on CBCT examination and Joint Space Index (JSI) analysis. The left and right JSI values of -38.5 and -52.6 indicated that the position of bilateral condyles had posterior displacement. Ten years prior to this evaluation, she underwent orthodontic treatment resulting in the extraction of two upper premolars and one lower central incisor. The joint symptoms, including pain and sounds, were alleviated along with verified mandibular forward repositioning by extraction of another lower central incisor. CONCLUSION: Mandibular backward positioning could be associated with TMD. JSI analysis based on CBCT is a convenient way to examine condylar positions quantitatively.

Design and Self-Assembly of Macrocycles with Metals at the Corners Based on Dissymmetric Terpyridine Ligands.

Terpyridine-based discrete supramolecular architectures with metal ions at the corners have rarely been reported. Herein, we report two dissymmetric terpyridyl ligands LA and LB decorated at the 5-position and 4-position of terpyridine respectively. The complexes constructed by the self-assembly of LA and LB with Zn(II) exhibit hand-circle-like structures. Moreover, all Zn(II) are successfully fixed in the corners. A series of dimeric to hexameric macrocycles is obtained by head-to-tail connections with changing concentration. This work will pave the way for preparation of more elaborate self-assembled structures based on dissymetric ligands.

[Orthodontic intrusion of the first and second mandibular molars with a vacuum-formed removable appliance: a case report].

This case report focused on a patient with supraeruption of the first and second mandibular molars as a result of loss of the first and second maxillary molars for a long time. We adopted a combination of a vacuum-formed removable appliance and elastics to intrude the first and second mandibular molars by using a continuous, light force to acquire sufficient restoration space for maxillary molars. Thus, the dental-implant treatment was successful, and a good and stable occlusal relationship was established.

[Effect of preoperative anxiety level on postoperative pain sensation in patients receiving implant denture for partial edentulism].

OBJECTIVE: To explore the effect of preoperative anxiety level on postoperative pain sensation in partially edentulous patients undergoing surgery for implant denture. METHODS: Eighty partially edentulous patients receiving implant denture were examined for preoperative anxiety level using State Trait Anxiety Inventory (STAI) and Modified Dental Anxiety Scale (MDAS) questionnaires before implantation surgery. The Visual Analogue Scale (VAS) and Present Pain Intensity (PPI) Questionnaire were used to assess the pain sensation in patients immediately after the operation. The correlations of preoperative state anxiety, trait anxiety, and dental anxiety with postoperative VAS score were analyzed. According to the assessment results of STAI, the patients were divided into little or no (score range 20-37) anxiety group (L group), moderate (38-44) anxiety group (M group), and high (45-80) anxiety group (H group) to analyze the effect of state anxiety and trait anxiety levels on postoperative pain sensation. RESULTS: Significantly positive correlations were found between preoperative state anxiety, trait anxiety and dental anxiety among the patients (P<0.01). Postoperative VAS score was positively correlated with trait anxiety score (P<0.01) and differed significantly between different trait anxiety groups (P<0.01). Compared with the patients in M and L groups, those in H group showed a significantly higher VAS score after the operation (P<0.05). CONCLUSION: The preoperative trait anxiety level is associated with postoperative pain sensation in partially edentulous patients receiving implant denture, suggesting the necessity of preoperative anxiety intervention in clinical practice.

Array and distribution of actin filaments in guard cells contribute to the determination of stomatal aperture.

Actin filaments in guard cells and their dynamics function in regulating stomatal movement. In this study, the array and distribution of actin filaments in guard cells during stomatal movement were studied with two vital labeling, microinjection of alexa-phalloidin in Vicia faba and expression of GFP-mTn in tobacco. We found that the random array of actin filaments in the most of the closed stomata changed to a ring-like array after stomatal open. And actin filaments, which were throughout the cytoplasm of guard cells of closed stomata (even distribution), were mainly found in the cortical cytoplasm in the case of open stomata (cortical distribution). These results revealed that the random array and even distribution of actin filaments in guard cells may be required for keeping the closed stomata; similarly, the ring-like array and cortical distribution of actin filaments function in sustaining open stomata. Furthermore, we found that actin depolymerization, the trait of moving stomata, facilitates the transformation of actin array and distribution with stomatal movement. So, the depolymerization of actin filaments was favorable for the changes of actin array and distribution in guard cells and thus facilitated stomatal movement.