Structuring restricted amorphous molecular chains in the reinforced cellulose film by uniaxial stretching.

The construction of the preferred orientation structure by stretching is an efficient strategy to fabricate high-performance cellulose film and it is still an open issue whether crystalline structure or amorphous molecular chain is the key factor in determining the enhanced mechanical performance. Herein, uniaxial stretching with constant width followed by drying in a stretching state was carried out to cellulose hydrogels with physical and chemical double cross-linking networks, achieving high-performance regenerated cellulose films (RCFs) with an impressive tensile strength of 154.5 MPa and an elastic modulus of 5.4 GPa. The hierarchical structure of RCFs during uniaxial stretching and drying was systematically characterized from micro- to nanoscale, including microscopic morphology, crystalline structure as well as relaxation behavior at a molecular level. The two-dimensional correlation spectra of dynamic mechanical analysis and Havriliak-Negami fitting results verified that the enhanced mechanical properties of RCFs were mainly attributed to the stretch-induced tight packing and restricted relaxation of amorphous molecular chains. The new insight concerning the contribution of molecular chains in the amorphous region to the enhancement of mechanical performance for RCFs is expected to provide valuable guidance for designing and fabricating high-performance eco-friendly cellulose-based films.

Hierarchically porous cellulose-based carbon aerogels with N-doped skeletons and encapsulated iron-based catalysts for efficient tetracycline catalytic degradation.

Three-dimensional interpenetrating and hierarchically porous carbon material is an efficient catalyst support in water remediation and it is still a daunting challenge to establish the relationship between hierarchically porous structure and catalytic degradation performance. Herein, a highly porous silica (SiO2)/cellulose-based carbon aerogel with iron-based catalyst (FexOy) was fabricated by in-situ synthesis, freeze-drying and pyrolysis, where the addition of SiO2 induced the hierarchically porous morphology and three-dimensional interpenetrating sheet-like network with nitrogen doping. The destruction of cellulose crystalline structure by SiO2 and the iron-catalyzed breakdown of glycosidic bonds synergistically facilitated the formation of electron-rich graphite-like carbon skeleton. The unique microstructure is confirmed to be favorable for the diffusion of reactants and electron transport during catalytic process, thus boosting the catalytic degradation performance of carbon aerogels. As a result, the catalytic degradation efficiency of tetracycline under light irradiation by adding only 5 mg of FexOy/SiO2 cellulose carbon aerogels was as high as 90 % within 60 min, demonstrating the synergistic effect of photocatalysis and Fenton reaction. This ingenious structure design provides new insight into the relationship between hierarchically porous structure of carbon aerogels and their catalytic degradation performance, and opens a new avenue to develop cellulose-based carbon aerogel catalysts with efficient catalytic performance.

Enhanced Dielectric Properties of All-Cellulose Composite Film via Modulating Hydroxymethyl Conformation and Hydrogen Bonding Network.

Cellulose-based dielectrics with attractive dielectric performance are promising candidates to develop eco-friendly electrostatic energy storage devices. Herein, all-cellulose composite films with superior dielectric constant were fabricated by manipulating the dissolution temperature of native cellulose, where we revealed the relationship among the hierarchical microstructure of the crystalline structure, the hydrogen bonding network, the relaxation behavior at a molecular level, and the dielectric performance of the cellulose film. The coexistence of cellulose I and cellulose II led to a weakened hydrogen bonding network and unstable C6 conformations. The increased mobility of cellulose chains in the cellulose I-amorphous interphase enhanced the dielectric relaxation strength of side groups and localized main chains. As a result, the as-prepared all-cellulose composite films exhibited a fascinating dielectric constant of as high as 13.9 at 1000 Hz. This work proposed here provides a significant step toward fundamentally understanding the dielectric relaxation of cellulose, thus developing high-performance and eco-friendly cellulose-based film capacitors.

Toward Excellent Energy Storage Performance via Well-Aligned and Isolated Interfaces in Multicomponent Polypropylene-Based All-Organic Polymer Dielectric Films.

Polypropylene (PP) serves as an excellent commercialized polymer dielectric film owing to its high breakdown strength, excellent self-healing ability, and flexibility. However, its low dielectric constant causes the large volume of the capacitor. Constructing multicomponent polypropylene-based all-organic polymer dielectric films is a facile strategy for achieving high energy density and efficiency simultaneously. Thereinto, the interfaces between the components become the key factors that determine the energy storage performance of the dielectric films. In this work, we propose to fabricate high-performance polyamide 513 (PA513)/PP all-organic polymer dielectric films via the construction of abundant well-aligned and isolated nanofibrillar interfaces. Laudably, a significant enhancement in the breakdown strength is achieved from 573.1 MV/m of pure PP to 692.3 MV/m with 5 wt % of PA513 nanofibrils. Besides, a maximum discharge energy density of about 4.4 J/cm2 is realized with 20 wt % of PA513 nanofibrils, which is about 1.6-folds higher than pure PP. Simultaneously, the energy efficiency of samples with modulated interfaces maintains higher than 80% up to 600 MV/m, which is much higher than pure PP of about 40.7% at 550 MV/m. This work provides a new strategy to fabricate high-performance multicomponent all-organic polymer dielectric films on an industrial scale.

Regenerated cellulose as template for in-situ synthesis of monoclinic titanium dioxide nanocomposite carbon aerogel towards multiple application in water treatment.

Immobilizing catalyst system faces the challenge of balancing catalysts stability and exposure of active site in water treatment. In this study, a novel in-situ synthesis of monoclinic phase of titanium dioxide (TiO2(B)) in cellulose-derived carbon aerogel (TCA) is proposed for processing multi-task in water treatment. The homogeneous gelation reaction supported the high dispersion of TiO2(B) in carbon skeleton. Meanwhile, TiO2 acts as crosslinker to reinforce cellulose network, then the grain refinement of amorphous TiO2 is limited to obtain TiO2(B) during carbonization. Benefiting from the reinforced structure, TCA remains the porous structure after carbonization and exposes more adsorption site than carbon aerogel blended with anatase particles (ACA). The adsorption performance of TCA are 837.3 mg/g, 1156.2 mg/g and 512.6 mg/g on methylene blue, malachite green and crystal violet, respectively. Compared with ACA, the superior interaction between TiO2 and graphite-like carbon improves the degradation rate of tetracycline from 1.3 × 10-3 min-1 to 8.6 × 10-3 min-1, and maintains the degradation efficiency in 3 rounds cyclic test. Besides, TCA also exhibits nearly twice to ACA on absorption capacity of different oil. This facile in-situ synthesis method offers a new insight in fabricating carbon aerogel immobilized photocatalysts system for multi-task in water treatment.

In-situ structuring a robust cellulose hydrogel with ZnO/SiO2 heterojunctions for efficient photocatalytic degradation.

Hydrogel supported photocatalyst, an efficient strategy for water remediation suffers from compromised catalytic activity and insufficient stability. Herein, a robust cellulose-based composite hydrogel with zinc oxide (ZnO)/silica (SiO2) heterojunctions were fabricated by in-situ synthesis, where SiO2 not only acted as a cross-linking agent to enhance the mechanical strength and stability of hydrogel, but also promoted the photocatalytic properties of ZnO via transferring the electron-hole pairs due to its surface state. As a result, a significant improvement in the mechanical properties of cellulose-based composite hydrogel was achieved, exhibiting a high compressive strength of 703.4 kPa. Moreover, the degradation efficiency of methylene blue (MB) under light irradiation by cellulose-based composite hydrogel was 95 % in 120 min and the removal ratio maintained as high as 90 % after eight degradation cycles. This study provides a low-cost and facile method to construct new hydrogel supports with high stability and efficient photocatalytic properties.

Durably Ductile, Transparent Polystyrene Based on Extensional Stress-Induced Rejuvenation Stabilized by Styrene-Butadiene Block Copolymer Nanofibrils.

The glassy polymer of polystyrene (PS) enjoys a good reputation as a promising optical material; however, the inherent brittleness hinders its further applications. Conventional toughening methods are realized based on the premise of a sacrifice in transparency and stiffness. In this work, we found an unprecedented strategy to address these obstacles by combining extensional stress-induced ductility and suppressing physical aging. PS-based film with a high stiffness, long-term ductility, and excellent transparency is achieved by introducing a styrene-butadiene block copolymer into the PS matrix and subsequently annealing stretched. A nanofibrillar structure of the polybutadiene (PB) phase is formulated surrounded by a PS matrix, and thus, the elongation at break enhances from 3.1% up to 86.8%, accompanying the yield strength enhanced from 25.5 to 62.2 MPa. More significantly, compared with neat PS, these films survive from physical aging and persistent ductility over time. The morphology deformation induced by stress makes an obvious contribution to the improvement of transparency. Investigating the dynamics of chain segments indicates that the incorporation of the copolymer can restrict rearrangement and local relaxation to the PS chain. This work could pave a potential route toward high-performance PS and might be transferable to other glassy polymers with a fragile character.

Intranasal Insulin Treatment Attenuates Metabolic Distress and Early Brain Injury After Subarachnoid Hemorrhage in Mice.

BACKGROUND: Intranasal administration of insulin to the brain bypasses the blood brain barrier (BBB) and can increase cerebral glucose uptake and prevent energy failure. Intranasal insulin treatment has shown neuroprotective effects in multiple central nervous system (CNS) lesions, but the effects of intranasal insulin on the metabolic and pathological process of subarachnoid hemorrhage (SAH) are not clear. This study is designed to explore the effects of intranasal insulin treatment on metabolic distress and early brain injury (EBI) after experimental SAH. METHODS: SAH model was built by endovascular filament perforation method in adult male C57BL/6J mice, and then, insulin was administrated via intranasal route at 0, 24, and 48 h post-SAH. EBI was assessed according to the neurological performance, BBB damage, brain edema, neuroinflammatory reaction, and neuronal apoptosis at each time point. To evaluate metabolic conditions, microdialysis was used to continuously monitor the real-time levels of glucose, pyruvate, and lactate in interstitial fluid (ISF) in living animals. The mRNA and protein expression of glucose transporter-1 and 3 (GLUT-1 and -3) were also tested by RT-PCR and Western blot in brain after SAH. RESULTS: Compared to vehicle, intranasal insulin treatment promoted the relative mRNA and protein levels of GLUT-1 in SAH brain (0.98 ± 0.020 vs 0.33 ± 0.016 at 24 h, 0.91 ± 0.25 vs 0.21 ± 0.013 at 48 h and 0.94 ± 0.025 vs 0.28 ± 0.015 at 72 h in mRNA/0.96 ± 0.023 vs 0.36 ± 0.015 at 24 h, 0.91 ± 0.022 vs 0.22 ± 0.011 at 48 h and 0.95 ± 0.024 vs 0.27 ± 0.014 at 72 h in protein, n = 8/Group, p < 0.001). Similar results were also observed in GLUT-3. Intranasal insulin reduced the lactate/pyruvate ratio (LPR) and increased ISF glucose level. It also improved neurological dysfunction, BBB damage, and brain edema and attenuated the levels of pro-inflammatory cytokines as well as neuronal apoptosis after SAH. CONCLUSIONS: The intranasal insulin treatment protects brain from EBI possibly via improving metabolic distress after SAH.

Structuring Hierarchically Porous Architecture in Biomass-Derived Carbon Aerogels for Simultaneously Achieving High Electromagnetic Interference Shielding Effectiveness and High Absorption Coefficient.

Developing high-performance electromagnetic interference (EMI) shielding materials with high absorption coefficient is highly desired for eliminating the secondary pollution of reflected electromagnetic wave (EMW). Nevertheless, it has long been a daunting challenge to achieve high shielding effectiveness (SE) and ultralow or no reflection SE simultaneously. Herein, highly porous and conductive carbon nanotube (CNT)-based carbon aerogel with a meticulously designed hierarchically porous structure from micro and sub-micro to nano levels is developed by specific two-stage pyrolysis and potassium hydroxide activation processes. The resultant activated cellulose-derived carbon aerogels (a-CCAs) exhibit an ultrahigh EMI SE of 96.4 dB in the frequency range of 8.2-12.4 GHz in conjunction with an exceptionally high absorption coefficient of 0.79 at a low density of 30.5 mg cm-3. The successful construction of hierarchically porous structure is responsible for the excellent "structurally absorbing" ability of a-CCAs, and the introduction of CNT-based heterogeneous conductive network can effectively dissipate the incident EMWs by interfacial polarization and microcurrent losses. Moreover, the as-prepared a-CCAs have a water contact angle of as high as 158.3°and a sliding angle of as low as 5.3°, revealing their superhydrophobic feature. The ingenious structure design proposed here provides a possible pathway to overcome the conflict between high EMI shielding performance and ultralow or no secondary reflection, and the as-prepared a-CCAs are exceedingly promising in the application of telecommunication, microelectronics, and spacecraft.

Hydrophobic Graphene Oxide as a Promising Barrier of Water Vapor for Regenerated Cellulose Nanocomposite Films.

Regenerated cellulose (RC) films exhibit poor water barrier performance, which seriously restricts its applications. To address this issue, an impermeable and hydrophobic graphene oxide modified by chemically grafting octadecylamine (GO-ODA) was utilized to enhance the water vapor barrier performance of RC nanocomposite films. Compared to the neat RC film, more than 20% decrease in the coefficient of water vapor permeability (P H2O) was achieved by loading only 2.0 wt % GO-ODA. The promising hydrophobicity of GO-ODA effectively retarded the formation of hydrogen bonding at the relatively weakened interface between GO and RC, compensating for the diffusion of water vapor molecules at the interface; on the other hand, the fully exfoliated GO-ODA nanosheets were inclined to align with the surface of the as-prepared RC nanocomposite films during hot-pressure drying, creating a much more tortuous pathway for diffusion of water molecules. The new insights could be valuable for widening application of cellulose such as packaging.

Interconnected Microdomain Structure of a Cross-Linked Cellulose Nanocomposite Revealed by Micro-Raman Imaging and Its Influence on Water Permeability of a Film.

Substantial adsorption of water vapor triggered by hydrogen-bonding interactions between water molecules and cellulose chains (or nanoplates) is hard to avoid in nanocomposite films, although the addition of nanoplates can improve the oxygen (or carbon dioxide) barrier property. In the present work, an effective strategy is raised to decline adsorption by weakening hydrogen-bonding interactions via chemical cross-linking by epichlorohydrin (ECH) without sacrificing the homogeneous dispersion of nanoplates. The generated microdomain structure of the chemical cross-linking reaction via ECH is explicitly revealed by micro-Raman imaging. Unambiguously, Raman maps of scanning elucidate the distribution and morphology of physical and chemical cross-linking domains quantitatively. The chemical cross-linking domains are nearly uniformly located in the matrix at a low degree of cross-linking, while the interconnected and assembled networks are formed at a high degree of cross-linking. ECH boosts the formation of chemical cross-linking microdomains, bringing out the terrific water vapor barrier property and alleviating the interfacial interactions in penetration, consequently magnifying the water contact angle and holding back the water vapor permeability. Our methodology confers an effective and convenient strategy to obtain remarkable water vapor-resistant cellulose-based films that meet the practical application in the packaging fields.

Robust cellulose nanocomposite films based on covalently cross-linked network with effective resistance to water permeability.

Cellulose films are of poor water-vapor barrier performance. Herein, we put forward an effective way to suppress adsorption by crosslinking of hydroxyl groups via epichlorohydrin (ECH), meanwhile graphene oxide (GO) nanosheets are utilized to prolong the pathway of vapor penetration. The strategy confers a significant enhancement of vapor barrier performance as well as mechanical properties to cellulose-based films. Specifically, an outstanding reduction of 67.4% in water-vapor permeability coefficient is achieved in nanocomposite films compared to the uncrosslinked cellulose films. Furthermore, for the first time, two-dimensional correlation analysis reveals that crosslinking of ECH do not alter penetration direction, while GO can eminently act as shielding for the formation of bound water which change the sequential order of firstly-interacted vapor area from crystalline to amorphous area. Free volume is the penetration destination. The retarding effect introduced by the GO in amorphous area gives rise to the improvement of the vapor-barrier.

Wearable Polyethylene/Polyamide Composite Fabric for Passive Human Body Cooling.

Personal cooling technologies (PCTs) locally control the temperature of an individual instead of a whole building and are thus energy saving. However, most PCTs still consume energy and are heavy in weight, restricting their application among human beings. To achieve personal thermal comfort and no energy consumption on hot summer days, we designed a bilayer structure fabric with high thermal comfort by increasing the dissipation of human thermal radiation and reducing solar energy absorption simultaneously. The fabric consisted of two layers, including a polyethylene film with nanopores (100-1000 nm in pore size) and a film made of nylon 6 nanofibers (ca. 100 nm in diameter) with beads (ca. 230 nm in diameter), which could increase the visible light reflectance but not affect the infrared wave radiation. Therefore, the designed fabric showed a high heat dissipation power, which was 14.13, 17.93, and 17.93 W/m2 higher than that of the selected traditional textiles of cotton, linen, and odile, respectively, suggesting good cooling capability. Its cooling performance was better than those reported by the previous research works even at a higher ambient temperature. Meanwhile, the moisture penetrability and hygroscopic property results indicated that the wearing comfort of the designed fabric reached the levels of the selected traditional textiles.

Ultralight Cellulose Porous Composites with Manipulated Porous Structure and Carbon Nanotube Distribution for Promising Electromagnetic Interference Shielding.

Lightweight conductive polymer composites based on biomass could be a promising candidate for electromagnetic interference (EMI) shielding application. Herein, tailoring porous microstructure and regulating the distribution of carbon nanotubes (CNTs) in cellulose composites are attempts to achieve highly efficient EMI shielding properties accompanying desired mechanical property and low density. Specifically, aligned porous structure is fabricated by ice-template freeze-drying method; meanwhile, CNT is regulated to decorate inside the cellulose matrix (CNT-matrix/cellulose porous composites) or to directly bind over the cellulose cell walls (CNT-interface/cellulose porous composites). It is found that, owing to the preferential distribution of CNT on the cell walls, the CNT-interface/cellulose porous composites possess a very high electrical conductivity of 38.9 S m-1 with an extremely low percolation threshold of 0.0083 vol % with regard to CNT-matrix/cellulose porous composites. Therefore, a shielding effectiveness of 40 dB with merely 0.51 vol % CNT under a thickness of 2.5 mm is achieved in CNT-interface/cellulose porous composites, which is attributed to efficient multiple reflections and the accompanying absorption with promoted conductivity and better-defined porous structure. More laudably, the CNT-interface/cellulose porous composites reveal a superior mechanical property with a specific modulus of 279 MPa g-1 cm3. The value behind the current work is to pave an effective way to fabricate environmentally benign, high-performance EMI shielding materials to practically boost numerous advanced applications of cellulose.

[Small interfering RNA-mediated α-enolase knockdown suppresses glycolysis and proliferation of human glioma U251 cells in vitro].

OBJECTIVE: To investigate the role of α-enolase (ENO1) in regulating glucose metabolism and cell growth in human glioma cells. METHODS: Glucose uptake and lactate generation were assessed to evaluate the changes in glucose metabolism in human glioma U251 cells with small interfering RNA (siRNA)-mediated ENO1 knockdown. MTT assay and 5-ethynyl-2'-deoxyuridine (EdU) staining were used to examine the cell growth and cell cycle changes following siRNA transfection of the cells. RESULTS: Transfection of U251 cells with siRNA-ENO1 markedly reduced glucose uptake (P=0.023) and lactate generation (P=0.007) in the cells and resulted in significant suppression of cell proliferation (*P<0.05) since the second day following the transfection. Transfection with siRNA-ENO1 also obviously suppressed cell cycle G1/S transition in the cells (P=0.0425). The expressions of HK2 and LDHA, the marker genes for glucose metabolism, were significantly down-regulated in the cells with siRNA-mediated ENO1 knockdown. CONCLUSION: ENO1 as a potential oncogene promotes glioma cell growth by positively modulating glucose metabolism.

Super-Robust Polylactide Barrier Films by Building Densely Oriented Lamellae Incorporated with Ductile in Situ Nanofibrils of Poly(butylene adipate-co-terephthalate).

Remarkable combination of excellent gas barrier performance, high strength, and toughness was realized in polylactide (PLA) composite films by constructing the supernetworks of oriented and pyknotic crystals with the assistance of ductile in situ nanofibrils of poly(butylene adipate-co-terephthalate) (PBAT). On the basis that the permeation of gas molecules through polymer materials with anisotropic structure would be more frustrated, we believe that oriented crystalline textures cooperating with inerratic amorphism can be favorable for the enhancement of gas barrier property. By taking full advantage of intensively elongational flow field, the dispersed phase of PBAT in situ forms into nanofibrils, and simultaneously sufficient row-nuclei for PLA are induced. After appropriate thermal treatment with the acceleration effect of PBAT on PLA crystallization, oriented lamellae of PLA tend to be more perfect in a preferential direction and constitute into a kind of network interconnecting with each other. At the same time, the molecular chains between lamellae tend to be more extended. This unique structure manifests superior ability in ameliorating the performance of PLA film. The oxygen permeability coefficient can be achieved as low as 2 × 10(-15) cm(3) cm cm(-2) s(-1) Pa(-1), combining with the high strength, modulus, and ductility (104.5 MPa, 3484 MPa, and 110.6%, respectively). The methodology proposed in this work presents an industrially scalable processing method to fabricate super-robust PLA barrier films. It would indeed push the usability of biopolymers forward, and certainly prompt wider application of biodegradable polymers in the fields of environmental protection such as food packaging, medical packaging, and biodegradable mulch.

Interleukin-16 polymorphism is associated with an increased risk of glioma.

OBJECTIVE: Previous studies have shown that interleukin (IL)-16 is overexpressed in human and rat gliomas. Potential links between IL-16 polymorphisms and glioma risk are currently unclear. The aim of this study was to investigate the association between IL-16 polymorphisms and glioma risk. METHODS: We examined IL-16 gene polymorphisms (i.e., rs 4778889, rs 11556218, and rs 4072111) in 216 patients with glioma and 275 controls in a Chinese population. Genotypes were determined using a polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) assay. Odds ratios (OR) and their corresponding 95% confidence intervals (CI) were used to evaluate the effect of the IL-16 polymorphisms on glioma risk. RESULTS: The rs 11556218TG genotype is associated with an increased risk of glioma compared with the TT genotype (OR=1.76; 95% CI, 1.22-2.54; p=0.002). Similarly, the rs 11556218G allele is associated with an increased risk of glioma compared with the T allele (OR=1.41; 95% CI, 1.06-1.87; p=0.017). However, no significant association was observed between the IL-16 rs 4778889 and rs 4072111 polymorphisms and the risk of glioma. CONCLUSION: These findings suggest that the IL-16 rs 11556218 polymorphism may be used as a susceptibility marker for glioma.

Poly(L-lactic acid) crystallization in a confined space containing graphene oxide nanosheets.

The semicrystalline polymer incorporated with nanofillers frequently exhibits complicated crystallization behavior, which is probably attributed to the nanofiller-constructed complex crystalline circumstance, especially a confined space. In the present work, in order to have a thorough understanding of biodegradable poly(L-lactic acid) (PLLA) crystallization behavior on the dependence of graphene oxide nanosheet (GONS) loadings, in particular the relatively high GONS loading, a set of GONS/PLLA nanocomposites with different GONS loadings ranging from 0 to 4.0 wt % were investigated in terms of isothermal crystallization behavior by differential scanning calorimetry and time-resolved Fourier-transform infrared spectroscopy techniques. The results indicated that GONSs not only served as heterogeneous nucleating agents for PLLA crystallization but also restricted the mobility and diffusion of PLLA chains. At low GONS concentrations of 0.25 and 0.5 wt %, GONSs acted as a temple for PLLA chains to land on due to extremely high specific surface area, thus promoting the conformational ordering and reducing the nucleating barrier. The nucleation effect of GONSs was dominant to achieve accelerated overall crystallization kinetics. As the GONS concentration rose up to 1.0 wt %, the GONS network was formed in the PLLA matrix, which was verified by solid-like rheological behavior at low frequencies in rheological measurement. The nanofiller network significantly constrained the mobility and diffusion of PLLA chains and offset the nucleation effect of GONSs, giving rise to a turning point in crystallization rate from promotion to restriction. Furthermore, a severely confined space was constructed by the more crowded and denser GONS networks at a higher GONS concentration of 4.0 wt %, compelling PLLA lamellae to grow in a two-dimensional mode. The unusual crystallization behavior of PLLA from promotion to restriction was also understood by the four-region model, in which the semiquantitative description of crystalline circumstance was provided. These results pave an effective way to further reveal the crystallization behavior of polymer at a relatively high nanofiller loading.