Gradient Hierarchically Porous Ionic-Junction Fibers of Wet-Spun Carboxymethyl Cellulose Coagulated with Copper Sulfate.

Polyelectrolyte-based ionic-junction fibers newly serve as signal transmission and translation media between electronic devices and biological systems, facilitating ion transport within organic matrices. In this work, we fabricated gel filaments of carboxymethyl cellulose (CMC) chelated with Cu(II) ions through wet-spinning, using a saturated coagulant of CuSO4. Interestingly, the as-spun fibers exhibited dramatic 3D porous frameworks that varied with the temperature and precursor concentration. At 20 °C, the Cu(II) chelation networks favored the formation of well-organized cellular chambers or corrugated channels, displaying dense stacking patterns. However, critical transitions from cellular chambers to corrugated channels occurred at precursor dope concentrations of approximately 2 and 7 wt %, with the porous structure diminishing beyond 8 wt %. We have proposed schematic diagrams to mimic the 3D pore structure, dense porous stacking, and formation mechanism, according to electronic micrographs. Our investigations revealed that the distinct ion-junction channels or chambers are under the control of axial drawing extension as well as the outside-inside penetration of Cu(II) ions into the dope and inside-outside diffusion of water into coagulants. Therefore, controlling the metal chelation-water diffusion process at specific temperatures and concentrations will offer valuable insights for tailoring ionic-junction soft filaments with gradient hierarchically porous structures and shape memory properties.

3-Dimentional printing of polysaccharides for water-treatment: A review.

Biological polysaccharides such as cellulose, chitin, chitosan, sodium alginate, etc., serve as excellent substrates for 3D printing due to their inherent advantages of biocompatibility, biodegradability, non-toxicity, and absence of secondary pollution. In this review we comprehensively overviewed the principles and processes involved in 3D printing of polysaccharides. We then delved into the diverse application of 3D printed polysaccharides in wastewater treatment, including their roles as adsorbents, photocatalysts, biological carriers, micro-devices, and solar evaporators. Furthermore, we assessed the technical superiority and future potential of polysaccharide 3D prints, envisioning its widespread application. Lastly, we remarked the challenging scientific and engineering aspects that require attention in the scientific research, industrial production, and engineering utilization. By addressing these key points, we aimed to advance the field and facilitate the practical implementation of polysaccharide-based 3D printing technologies in wastewater treatment and beyond.

Recurrence of Submandibular Adenocarcinoma with Intra-cranial Metastasis as the First Symptom.

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Experiment Study on the Effect of Aluminum Sulfate-Based Alkali-Free Accelerator and the w/c on Cement Hydration and Leaching.

The alkali-free accelerator based on aluminum sulfate is widely used in shotcrete in tunnels. Long-term Ca-leaching of shotcrete may adversely affect the tunnels in a water-rich mountain. It is necessary to examine further the impact of the AS accelerator and w/c on cement hydration and leaching. In this study, all the cement pastes were cured in the environment with R.H. > 95% and 20 ± 1 °C for 60 days and leached in a running water test with 6 M NH4Cl at 1 cm/s. The hydration kinetics was characterized by isothermal calorimetry. Additionally, the microstructural and mineralogical alterations were characterized by XRD, SEM, MIP, and N2 absorption. The results show that (1) the AS accelerator affected the hydration kinetics of cement by stimulating early hydration and delaying the late silicate hydration, resulting in AS-accelerated cement pastes with rougher pore structure. As a result, the higher the dose of AS accelerator, the faster the cement pastes will leach. (2) Hydration kinetics of the accelerated cement are not affected by the w/c. The AS-accelerated cement pastes with lower w/c have a denser pore structure. So, the reduction in the w/c contributes to leaching resistance.

Macroscopic Spiral Patterns of Cholesteric Cellulose Nanocrystals Induced by Chiral Doping and Vortex Flowing.

Negatively surface-charged sulfate cellulose nanocrystals (CNCs) are always slowly self-assembled into left-handed cholesteric mesophases. In this work, macroscopic spiral patterns induced by counterclockwise vortex flowing or chiral doping were investigated. Results show that iridescent patterns of the arithmetic spiral, rose spiral, or latitude ripples were generated under the vortex rotation, indicating a severe microphase separation of CNCs. Moreover, the spiral pattern and rotational symmetry were highly correlated to the twisting and flowability of CNCs as well as chiral dopants. Alternatively, the cholesteric pitch and maximum reflective wavelength (λmax) of CNCs were strongly increased by sinistral dopants other than the dextral ones, indicating an enhanced torsion of left-handed CNC mesophases by the dextral dopants. In addition, macroscopic spiral patterns distinctly existed in dextrally doped CNCs owing to a synergistic chiral enhancement. Therefore, the mechanochiral or chemical chiral transition from microscopic twisting to macroscopic spiral provides a potential inspiration for chiral self-organization of biological macromolecules.

Sustainable iridescence of cast and shear coatings of cellulose nanocrystals.

As an eco-friendly sustainable iridescent coating, cholesteric cellulose nanocrystal (CNC) is susceptible to substrate effects or shearing effects. In this work, interface interaction and liquid crystal phase transition were evaluated for fabricating iridescent cast or shear coatings of CNCs onto substrates of polystyrene, glass, ceramic, wood, stainless steel, metal, or metal alloy. Three types of substrate effects and four categories of shearing effects on the structure color mechanism of CNC coatings were proposed. Practically, several efficient approaches, such as increasing colloidal concentration, enhancing water-retention of substrates, raising processing temperature, slowing down shearing speed, or doping functional additives were involved. Hence, a feasible strategy was provided for preparing sustainable, iridescent, stable, and industrially scalable coatings of CNCs.

Nicotinic Acetylcholine Receptor α7 Subunit Is an Essential Regulator of Seizure Susceptibility.

A large body of data has confirmed that α7 nicotinic acetylcholine receptors (nAChRs) play a pivotal role in cognition, memory, and other neuropsychiatric diseases, but their effect on seizure susceptibility in C57BL/6 wild-type mice is not fully understood. Here, we showed that decreased activity of α7 nAChRs could increase the excitability of CA1 pyramidal neurons and shorten the onset time of epilepsy in pilocarpine-induced mouse models. However, compared with the control group, there was no apparent effect of increasing the activity of α7 nAChRs. Moreover, the expression of α7 nAChRs is downregulated in human epileptogenic tissues. Taken together, our findings indicate that α7 nAChR is an essential regulator of seizure susceptibility.

Liquid Transport in Fibrillar Channels of Ion-Associated Cellular Nanowood Foams.

A mechanical disintegration of waste wood biomass and freeze-induced assembly of colloidal nanowood were effectively deployed to explore ion-associated cellular foams (NWFs) with unidirectional channels. Under the assistance of inorganic ions, the as-fabricated foams were significantly enhanced in physical stability, compressive strength, flame retardancy, and thermal barrier, accounting for the tuning effects of pores and channels, surface charges, and microphase interaction by ion effects and freeze orientation. As a result, the vascular-like ion-doped channels benefited from quick capillary liquid transport. Under 1 sun illumination, NWF-V as a 3-D evaporator exhibited a high evaporation rate of 1.50 kg m-2 h-1 and a conversion efficiency of up to 88.9% for seawater desalination. Dramatically, an average of 12.5 kg m-2 of fresh water could be generated on each sunny day by outdoor NWFs for durability beyond 15 days. Under the drive of fuel combustion, an efficient conveying of ethanol or pump oil could be at rates of 0.44 and 0.26 mL min-1, respectively. Moreover, combustion flame with variable color was generated according to the doping cations in NWFs. Therefore, sustainable, green, facile, and multifunctional wood-based cellular foams could be tailored, scaled-up, and applied as color flame burners or desalination evaporators under combustion or solar drive in the energy and environment fields.

Mechanical Characteristics of Cement-Based Grouting Material in High-Geothermal Tunnel.

The cement-based grouting materials used for practical purposes in high-geothermal tunnels are inevitably affected by humidity and high temperature, leading to the deterioration of mechanical properties. Based on the characteristics of changing high temperatures and two typical conditions of hot-humid and hot-dry environments in high-geothermal tunnels, many mechanical strength tests were carried out on the grouting material cured under different environmental conditions. The study results indicated that high temperature and low relative humidity were unfavorable to the development of mechanical characteristics of grouting material, but the coupling effect of two factors could improve the strength at early ages and reduce the degradation of long-term strength. As the curing temperature exceeded 56.3 °C, the humidity effect on strength played a more important role in recovering the strength of grouting material damaged by high temperature. Temperature had more significant impact on the relative peak stress while the relative humidity had greater influence on the relative peak strain. A calculation compressive constitutive model was prospered, which considering both temperature and relative humidity. The study results may provide much valuable experimental data and theoretical supporting for the design of compression constitutive of cement-based grouting material in high-geothermal tunnel.

Mesophase transition of cellulose nanocrystals aroused by the incorporation of two cellulose derivatives.

Cellulose nanocrystals (CNCs) per their twisting structure and high aspect ratio and charged surface property are increasingly receiving great attention in chiral photonic crystal and pigment fabrication. However, the cholesteric mesophases of CNCs is unstable and easily destroyed by the additives with high Mw. In this work, hydroxypropyl cellulose (HPC) and carboxymethyl cellulose (CMC) are incorporated into CNCs for a continuous mesophase transition monitoring. We investigated the effects of HPC and CMC on the properties of CNCs with respect to the morphology, mesophase, rheology, and structure-color properties. Our results showed that the addition of CMC (≥ 1 wt%) prevented the formation of a continuous cholesteric phase but resulting in a fast gelation due to the strong repulsion between CMC and CNCs. Alternatively, the cholesteric phase was well-preserved in the CNC/HPC in which HPC (< 10 wt%) served as an efficient tuner of phase transition, color hue and rheology properties.

Chromium (III) coordination capacity of chitosan.

Polycationic chitosan has a strong coordination to heavy metal ions due to its multifunctional hydroxyl and amino groups. However, due to the fast and facile dissolution of chitosan in acidic medium, it is difficult to measure the exact adsorption amount or coordination capacity accurately. In this work, a simple method of lyophilization plus ethanol-washing was employed to separate and purify chitosan/Cr(III) complex for further determining the coordination capacity. Meanwhile, the coordination structure of Bridge-chitosan-N(OH)3(H2O) and morphology of regenerated fibrillar sponge of CS/Cr(III) were further certified. The coordination capacity of Cr(III) on chitosan increased with the rising concentration of Cr(III) ions till the maximum coordination capacity was reached up to 355.03 mg/g. The mechanisms and characteristic parameters of the adsorption process were fit using two-parameter isotherm models which revealed the following order (based on the coefficient of determination) of Langmuir > Halsey > Freundlich > Temkin > Dubinin-Radushkevich. A proposed coordination formula of CS/Cr (III) might be a good certificate for the homogeneous chemical combination nature of Cr(III) on the monolayer surface of chitosan in a molecular scale.

Discovery of 5-Signature Predicting Survival of Patients with Lower-Grade Glioma.

OBJECTIVE: In the study, we aimed to identify key microRNAs (miRNAs) and clinical factors associated with survival time of lower-grade glioma (LGG) and develop an expression-based miRNA signature to provide survival risk prediction for patients with LGG. METHODS: We obtained miRNA expression profiles and clinical information of patients with LGG from The Cancer Genome Atlas dataset. All 591 miRNAs were modeled using random Forest Survival, Regression, and Classification to construct a random forest model for survival analysis, and feature selection was performed. We used univariate and multivariate Cox regression analysis to screen differentially expressed miRNAs and clinical factors related to overall survival of patients with LGG. RESULTS: A total of 591 differentially expressed miRNAs were obtained between LGG and normal tissues. After univariate and multivariate Cox regression analysis, 2 predictive miRNAs (hsa-miR-10b-5p and hsa-miR-15b-5p) and 3 clinical factors (grade, age, and cancer status) were finally screened out to construct a 5-signature, based on which patients in the training dataset were divided into high-risk and low-risk groups. The competitive performance of the 5-signature was revealed by receiver operating characteristic curve analysis. The prognostic value of the 5-signature was successfully validated in the testing and validation dataset. CONCLUSIONS: Our study demonstrated the promising potential of the novel 5-signature as an independent biomarker for survival prediction of patients with LGG.

Lyotropic liquid crystal self-assembly of H2O2-hydrolyzed chitin nanocrystals.

H2O2 hydrolysis of mechanically-defibrillated chitin nanofibrils was explored as a green way of fabricating rod-like chitin nanocrystals (H2O2-hydrolyzed CHNs) that have an average length of 350 nm and width of 40 nm. We investigated the structure and morphology of CHNs as well as the rheology and lyotropic self-assembly behavior of its colloidal dispersions. The results show that although H2O2-hydrolyzed CHNs maintained the crystalline structure of α-chitin, surface charge of the nanorods was switched from positive to negative. As a consequence, the colloidal nanocrystals were well-dispersed in neutral or alkaline aqueous media, and behaved as a lyotropic liquid crystal between two critical concentrations. It is interesting that lyotropic liquid crystal transition was a spontaneously self-assembly from well-aligned nanofibers, to nanobelts, and to multi-layered lamellae. At high critical concentration, H2O2-hydrolyzed CHN colloids exhibited a sol-gel transition, which was discovered to be highly dependent on the storage time, concentration, temperature, and surface charge density. It is also suggested that nematic mesophases rather than gel could be effectively maintained by improving the surface charge density or lowering the aging temperature and colloidal concentration of CHNs.

Fiber Alignment and Liquid Crystal Orientation of Cellulose Nanocrystals in the Electrospun Nanofibrous Mats.

Sulfate cellulose nanocrystal (CNC) dispersions always present specific self-assembled cholesteric mesophases which is easily affected by the inherent properties of particle size, surface charge, and repulsion or affinity interaction, and external field force generated from ionic potential of added electrolytes, magnetic or electric field, and mechanical shearing or stretching. Aiming at understanding the liquid crystal orientation and fiber alignment under high-voltage electric field, randomly distributed, uniform-aligned, or core-sheath nanofibrous mats involving charged CNCs and PVA were electrospun; and among them, specific straight arrayed fine nanofibers with average diameter of 270 nm were manufactured by using a simple and versatile gap collector. Moreover, arrayed composite nanofibers regularly aligned along the vertical direction of gap plates and selectively reflected frequent and continuous birefringence which was regarded as nematic phases of CNCs induced by the uniaxial stretching under high-voltage electric field. As a synergic effect of rigidness of nanocrystals and stretching orientation of nematic phases, the aligned nanofibrous arrays exhibited a higher tensile strength and strain than the randomly oriented or core-sheath nanofibrous mats at the same loading of CNCs. By contrast, mesophase transition of CNCs from cholesteric to nematic occurred in the coaxially spun core-sheath nanofibers at a loss of long-ranged chiral twist. Hence, the structure-effect relationship between liquid crystal orientation of charged nanorods in polymer-based fine nanofibers and the flexibility or mechanical integrity of the aligned fiber array will be favorable for strategic development of functional liquid crystal fabrics.

Carbon materials derived from chitosan/cellulose cryogel-supported zeolite imidazole frameworks for potential supercapacitor application.

In order to promote sustainable development, green and renewable clean energy technologies continue to be developed to meet the growing demand for energy, such as supercapacitor, fuel cells and lithium-ion battery. It is urgent to develop appropriate nanomaterials for these energy technologies to reduce the volume of the device, improve the efficiency of energy conversion and enlarge the energy storage capacity. Here, chitosan/cellulose carbon cryogel (CCS/CCL) were designed and synthesized. Through the introduction of zeolite imidazole frameworks (ZIFs) into the chitosan/cellulose cryogels, the obtained materials showed a microstructure of ZIF-7 (a kind of ZIFs) coated chitosan/cellulose fibers (CS/CL). After carbonizing, the as-prepared carbonized ZIF-7@cellulose cryogel (NC@CCL, NC is carbonized ZIF-7) and carbonized ZIF-7@chitosan cryogel (NC@CCS) exhibited suitable microspore contents of 34.37% and 30%, respectively, and they both showed an internal resistance lower than 2Ω. Thereby, NC@CCL and NC@CCS exhibited a high specific capacitance of 150.4Fg-1 and 173.1Fg-1, respectively, which were much higher than those of the original materials. This approach offers a facile method for improving the strength and electronic conductivity of carbon cryogel derived from nature polymers, and also efficiently inhibits the agglomeration of cryogel during carbonization in high temperature, which opens a novel avenue for the development of carbon cryogel materials for application in energy conversion systems.

Vapor sensing with color-tunable multilayered coatings of cellulose nanocrystals.

Colloidal cellulose nanocrystals were LBL deposited to form firmly-stacked optical coatings in which the nanorods regulated their head-to-tail association and aligned in the axial-centrifuged direction. The periodically transition from blue to orange of reflected colors was tunable via deposition layer adjustment. While the sensing coating was exposed to vapors of NH3.H2O, H2O, HCl and HAc, respectively, the color variation in the response process was irreversible at room temperature and highly dependent on vapor diffusion and chemical interface interaction. Consequently, HAc vapor presented the longest sensing transition of wavelength, whereas the alkaline NH3.H2O displays a less recovery ratio than HAc and H2O at room temperature. Under heating at 50°C, the sensed coatings could mostly be restored to their original state except HCl-etched one. Therefore, the naked-eyed qualitative detectability of vapors by nanocellulose could be realized by the divergence in color shift which is of great importance in chemical sensors.

Cholesteric film of Cu(II)-doped cellulose nanocrystals for colorimetric sensing of ammonia gas.

With the increasing demand of environmental monitoring for toxic and odorous ammonia gas it is desired to develop specific green, cost-effective and in situ passive colorimetric alternatives to current complex instrumentations. In this work, we designed an ammonia gas sensor based on cholesteric liquid crystal films of copper(II)-doped cellulose nanocrystals (CNCCu(II)) whose structure, optical and sensing properties were investigated. The hybrid films using the low doping Cu(II) as a color-tuning agent inherited the chiral nematic signature and optical activity of CNCs, suggesting a strong chelation between copper ions and negatively charged CNCs. The sensing performance illustrates that the CNCCu(II)125 film was sensitive to ammonia gas which could merge into nematic layers of CNCs and trigger-sensed to copper ions chelated on CNCs, consequently arousing a red-shift of reflective wavelength as well as an effective colorimetric transition. Such a hybrid film is anticipated to boost a new gas sensing regime for fast and effective on-site qualitative investigations.

Phosphate adsorption and precipitation on calcite under calco-carbonic equilibrium condition.

Phosphate (PO43-) removal on calcite often entails two processes: adsorption and precipitation. Separating these two processes is of great importance for assessment of PO43- stability after removal. Thus, this study was aimed at finding a critical range of conditions for separating these two processes in calco-carbonic equilibrium, by adjusting PO43- concentration, reaction time and pH. PO43- removal kinetic results showed that: (I) At pH7.7, PO43- removal was mainly by adsorption at initial PO43- concentration ≤2.2 mg L-1 and reaction time ≤24 h, with dominant precipitation occurring at initial PO43- concentration ≥3 mg L-1 after 24 h reaction; (II) At pH8.3, adsorption was the key removal process at initial PO43- concentration ≤7.5 mg L-1 and reaction time ≤24 h, whereas precipitation was observed at initial PO43- concentration of 10 mg L-1 after 24 h reaction, (III) At pH 9.1 and 10.1, PO43- removal mechanism was mainly by adsorption at initial PO43- concentration ≤10 mg L-1 within 24 h reaction. Based on the kinetic results, it is suggested that PO43- precipitation will occur after 24 h reaction when saturation index of amorphous calcium phosphate is between 1.97 and 2.19. Besides, increasing PO43- concentration does not cause a continuous decline of PO43- removal percentage. Moreover, experimental removal data deviated largely from the theoretical adsorption value by CD-MUSIC model. These indicate occurrence of precipitation which is in agreement with the kinetic result. Therefore our study will provide fundamental reference information for better understanding of phosphorous stabilization after removal by calcite.

Microfibrillar Polysaccharide-Derived Biochars as Sodium Benzoate Adsorbents.

Microfibrillar biochars of chitin (CTF), chitosan (CSF), and cellulose (CLF) were fabricated via green homogenization and a pyrolysis process, and were subsequently explored as adsorbents for removing over-released sodium benzoate (SB) in aqueous systems. The structure, composition, morphology, and adsorption behavior of the as-fabricated biochars were characterized. Results suggest that all biochars, with a microscaled fibrillar structure and foam-like network morphology, underwent severe chemical transition during the pyrolysis process, thereby causing an enhancement of the Brunauer-Emmett-Teller surface area, pore volume, and aromatic and carbonaceous composition. Consequently, N-doped porous CTF/CSF microfibrillar biochars displayed a distinguished capture capacity toward SB compared to that of their fibrillar precursors. Tailoring the chemical composition, porous structure, and sorption mechanism constitutes a possible strategy to achieve adequate structural effects of polysaccharide microfibrillar chars for potential application in environmental treatment or bioenergy.

Cellulose Nanocrystal/Poly(ethylene glycol) Composite as an Iridescent Coating on Polymer Substrates: Structure-Color and Interface Adhesion.

The broad utility as an environmentally friendly and colorful coating of cellulose nanocrystal (CNC) was limited by its instability of coloration, brittleness, and lack of adhesion to a hydrophobic surface. In the present work, a neutral polymer, poly(ethylene glycol) (PEG) was introduced into CNC coatings through evaporation-induced self-assembly (EISA) on polymer matrices. The structure-color and mechanical properties of the composite coating or coating film were characterized by UV-vis spectroscopy, polarized light microscopy (PLM), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WXRD), and tensile tests. Results showed that the reflective wavelength of the iridescent CNCs could be finely tuned by incorporation of PEG with varied loadings from 2.5 to 50 wt %, although the high loading content of PEG would produce some side effects because of the severe microphase separation. Second, PEG played an effective plasticizer to improve the ductility or flexibility of the CNC coating or coating film. Furthermore, as a compatibilizer, PEG could effectively and tremendously enhance the adhesion strength between CNCs and neutral polymer matrices without destroying the chiral nematic mesophases of CNCs. Environmentally friendly CNC/PEG composites with tunable iridescence, good flexibility, and high bonding strength to hydrophobic polymer matrices are expected to be promising candidates in the modern green paint industry.