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The combustion agglomeration of nano-aluminum (nAl) powder leads to incomplete combustion, which seriously hinders its application as metal fuel. In this work, nAl@AlF3 composites were produced by coating nAl with AlF3via a facile chemical deposition method. TEM and SEM analyses indicated that the AlF3 layer was evenly coated on the surface of nAl with a thickness of 4.6-9.1 nm, thereby varying the quantity of AlF3 applied. Experimental results from combustion indicated that the prepared nAl@AlF3 composites exhibit superior combustion efficiency, a higher combustion rate, and reduced combustion agglomeration as compared to raw nAl. Contrary to the widely accepted explanation that volatilization of AlF3 hinders Al combustion agglomeration, we proved that the gas-solid reaction between nAl and AlF3 plays an important role in inhibiting the sintering of nAl particles produced. The gaseous intermediate (i.e., AlOF and HF) released from the hydrolysis of AlF3 could reduce the diffusion barrier of Al2O3 to facilitate the reaction of Al core, which enhances the combustion reaction kinetics. More importantly, these gaseous products actively participate in the reaction cycle to continuously exert their catalytic effects.
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The fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one-step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation-growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length-dependent toughening effect.
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The self-assembly morphologies of subunits are largely governed by thermodynamics, which plays a less important role in dimensional control. Particularly for one-dimensional assemblies from block copolymers (BCPs), the negligible energy difference between short and long ones imposes great challenges in length control. Herein, we report that by incorporating additional polymers to induce in situ nucleation and trigger the subsequent growth, controllable supramolecular polymerization driven by mesogenic ordering effect could be realized from liquid crystalline BCPs. The length of the resultant fibrillar supramolecular polymers (SP) is controlled by tuning the ratio between nucleating and growing components. Depending on the choice of BCPs, the SPs can be homopolymer-like, heterogeneous triblock, and even pentablock copolymer-like. More interestingly, with insoluble BCP as a nucleating component, amphiphilic SPs are fabricated, which can undergo spontaneous hierarchical assembly.
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Azide compounds are widely used and especially, polymers bearing pendant azide groups are highly desired in numerous fields. However, harsh reaction conditions are always mandatory to achieve full azidation, causing severe side reactions and degradation of the polymers. Herein, we report the design and preparation of two azide ionic liquids (AILs) with azide anion and triethylene glycol (E3 )-containing cation, [P444E3 ][N3 ] and [MIME3 ][N3 ]. Compared with the traditional sodium azide (NaN3 ) approach, both AILs showed much higher reaction rates and functional-group tolerance. More importantly, they could act as both reagents and solvents for the quantitative azidation of various polymeric precursors under mild conditions. Theoretical simulations suggested that the outstanding performance of AILs originated from the existence of ion pairs during the reaction, and the E3 moieties played a crucial role. Lastly, after the reaction, the AILs could be easily regenerated, presenting a safer, greener, and highly efficient synthesis route for azide polymers.
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Self-assembly to build high-level structures, which is ubiquitous in living systems, has captured the imagination of scientists, striving to emulate the intricacy, homogeneity and versatility of the naturally occurring systems, and to pursue a similar level of organization in artificial building blocks. In particular, self-sorting assembly in multicomponent systems, based on the spontaneous recognition and consequent spatial aggregation of the same or interactive building units, is able to realize very complicated assembly behaviours, and usually results in multiple well-ordered products or hierarchical structures in a one-step manner. This highly efficient assembly strategy has attracted tremendous research attention in recent years, and numerous examples have been reported in artificial systems, particularly with supramolecular and polymeric building blocks. In the current review, we summarize the progress in recent years, and classify them into five main categories, based on their working mechanisms or principles. With the review of these strategies, we hope to provide not only some deep insights into this field, but also and more importantly, useful thoughts in the design and fabrication of self-sorting systems in the future.
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Polímeros , Polímeros/químicaRESUMEN
Achieving full-color emission from a single chromophore is not only highly desirable from practical considerations, but also greatly challenging for fundamental research. Herein, we demonstrated the density-dependent emission colors from a single boron-containing chromophore, from which multi-color fluorescent polyurethanes were prepared as well. Originating from its switchable molecular conformations, the emission color of the chromophore was found to be governed by the packing density and strongly influenced by hydrogen bonding interactions. The chromophore was incorporated into polyurethanes to achieve full-color emitting materials; the emission color was only dependent on the chromophore density and could be tuned via synthetic approach by controlling the compositions. The emission colors could also be modulated by physical approaches, including by swelling/deswelling process, compression under high pressure, and even blending the fluorescent polyurethane with non-emitting ones.
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Polymeric materials that simultaneously possess excellent mechanical properties and high self-healing ability at room temperature, convenient healing, and facile fabrication are always a huge challenge. Herein, we report on surface-energy-driven self-healing energetic linear polyurethane elastomers (EPU) that were facilely fabricated by two-step methods to acquire high healing efficiency and mechanical properties. By constructing surface energy and dynamic hard domains, energetic linear polyurethane elastomers not only obtained high healing ability and mechanical properties at high or room temperature but also avoid the use of some assisted healing conditions and complex chemical structure design and decrease manufacturing difficulty. Based on the interfacial healing physical model, various trends of surface tension, radius, and depth of the crack bottom were calculated to analyze the healing mechanism. We propose that polyurethane elastomers with low junction density could generate excess surface energy resulting from damage and drive self-healing, and incorporating a small amount of disulfide bonds increases the slightly packed hard phase and decreases the healing energy barrier. This work may offer a novel strategy for improving mechanical tensile and healing ability in the field of self-healing material application.
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Geometric structures are commonly encountered in natural and designed systems. However, the bottom-up fabrication of regular geometric assemblies with precise dimensional control, especially from soft materials, poses an outstanding challenge in contemporary materials science and chemistry. Herein, we present a general method for the preparation of colloidally stable, hexagonal platelets via the formation of crystalline inclusion complexes of tris-o-phenylenedioxycyclotriphosphazene and block copolymers bearing interactive blocks. Dictated by the screw dislocation growth of inclusion complexes, uniform hexagonal platelets with precisely controllable dimensions can be prepared. This supramolecular assembly approach is further utilized to produce concentric hexagonal platelets via stepwise seeded growth from various inclusion complexes.
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Cristalización/métodos , Polímeros/química , Sistemas de Liberación de Medicamentos , Microscopía Electrónica de Transmisión , Propiedades de SuperficieRESUMEN
BACKGROUND & AIMS: Focal zone 1 steatosis, although rare in adults with nonalcoholic fatty liver disease (NAFLD), does occur in children with NAFLD. We investigated whether focal zone 1 steatosis and focal zone 3 steatosis are distinct subphenotypes of pediatric NAFLD. We aimed to determine associations between the zonality of steatosis and demographic, clinical, and histologic features in children with NAFLD. METHODS: We performed a cross-sectional study of baseline data from 813 children (age <18 years; mean age, 12.8 ± 2.7 years). The subjects had biopsy-proven NAFLD and were enrolled in the Nonalcoholic Steatohepatitis Clinical Research Network. Liver histology was reviewed using the Nonalcoholic Steatohepatitis Clinical Research Network scoring system. RESULTS: Zone 1 steatosis was present in 18% of children with NAFLD (n = 146) and zone 3 steatosis was present in 32% (n = 244). Children with zone 1 steatosis were significantly younger (10 vs 14 years; P < .001) and a significantly higher proportion had any fibrosis (81% vs 51%; P < .001) or advanced fibrosis (13% vs 5%; P < .001) compared with children with zone 3 steatosis. In contrast, children with zone 3 steatosis were significantly more likely to have steatohepatitis (30% vs 6% in children with zone 1 steatosis; P < .001). CONCLUSIONS: Children with zone 1 or zone 3 distribution of steatosis have an important subphenotype of pediatric NAFLD. Children with zone 1 steatosis are more likely to have advanced fibrosis and children with zone 3 steatosis are more likely to have steatohepatitis. To achieve a comprehensive understanding of pediatric NAFLD, studies of pathophysiology, natural history, and response to treatment should account for the zonality of steatosis.
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Hígado Graso/etiología , Hígado Graso/patología , Cirrosis Hepática/complicaciones , Cirrosis Hepática/patología , Enfermedad del Hígado Graso no Alcohólico/complicaciones , Adolescente , Biopsia , Niño , Estudios Transversales , Femenino , Hepatitis C , Histocitoquímica , Humanos , MasculinoRESUMEN
Constructing unique mesoporous 2D Si nanostructures to shorten the lithium-ion diffusion pathway, facilitate interfacial charge transfer, and enlarge the electrode-electrolyte interface offers exciting opportunities in future high-performance lithium-ion batteries. However, simultaneous realization of 2D and mesoporous structures for Si material is quite difficult due to its non-van der Waals structure. Here, the coexistence of both mesoporous and 2D ultrathin nanosheets in the Si anodes and considerably high surface area (381.6 m2 g-1 ) are successfully achieved by a scalable and cost-efficient method. After being encapsulated with the homogeneous carbon layer, the Si/C nanocomposite anodes achieve outstanding reversible capacity, high cycle stability, and excellent rate capability. In particular, the reversible capacity reaches 1072.2 mA h g-1 at 4 A g-1 even after 500 cycles. The obvious enhancements can be attributed to the synergistic effect between the unique 2D mesoporous nanostructure and carbon capsulation. Furthermore, full-cell evaluations indicate that the unique Si/C nanostructures have a great potential in the next-generation lithium-ion battery. These findings not only greatly improve the electrochemical performances of Si anode, but also shine some light on designing the unique nanomaterials for various energy devices.
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Silicon is a promising alternative anode material since it has a ten times higher theoretical specific capacity than that of a traditional graphite anode. However, the poor cycling stability due to the huge volume change of Si during charge/discharge processes has seriously hampered its widespread application. To address this challenge, we design a silicon hollow sphere nanostructure by selective etching and a subsequent magnesiothermic reduction. The Si hollow spheres exhibit enhanced electrochemical properties compared to the commercial Si nanoparticles. The initial discharge and charge capacities of the Si hollow sphere anode are 2215.8 mAh g-1 and 1615.1 mAh g-1 with a high initial coulombic efficiency (72%) at a current density of 200 mA g-1, respectively. In particular, the reversible capacity is 1534.5 mAh g-1 with a remarkable 88% capacity retention against the second cycle after 100 cycles, over four times the theoretical capacity of the traditional graphite electrode. Therefore, our work demonstrates the considerable potential of silicon structures for displacing commercial graphite, and might open up new opportunities to rationally design various nanostructured materials for lithium ion batteries.
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BACKGROUND: Suboptimal asthma control during pregnancy may impact perinatal outcomes. U.S. guidelines recommend questionnaires to assess asthma control including the Asthma Control Test (ACT). It is unknown in a research setting to what extent recall differs by the time between symptom occurrence and the administration of the questionnaire. METHODS: Between 2009-2014, 196 pregnant asthmatic women were recruited by the Organization of Teratology Information Specialists (OTIS) MotherToBaby Pregnancy Studies. Participants were administered the ACT at enrollment, gestational weeks 20 and 32, and shortly after delivery. The same women were also administered the ACT retrospectively at approximately 6 months postpartum. RESULTS: The Pearson correlation coefficients between the in-pregnancy and retrospective continuous ACT scores for the 1st, 2nd and 3rd trimesters were: 0.67 (95% CI: 0.58, 0.74), 0.61 (0.52, 0.70) and 0.65 (0.56, 0.72), respectively. When dichotomized into well-controlled asthma (ACT score ≥ 20) versus otherwise, the chi-square test for all three trimesters resulted in p values <0.0001. Cohen's Kappa statistics for the same dichotomized scores were 0.51, 0.45 and 0.40 for each trimester respectively. There was no evidence that adverse outcome of pregnancy (recall bias) influenced postpartum responses. CONCLUSIONS: The retrospectively recalled ACT score obtained postpartum was substantially different compared to in-pregnancy administration of the same questionnaire which could reflect test-retest variability as well as attenuation of recall. Documentation of the magnitude and direction of these differences could be useful in interpretation of the impact of asthma control when the ACT is used in retrospective case-control studies for pregnancy outcomes.
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Asma/fisiopatología , Recolección de Datos/métodos , Recolección de Datos/normas , Complicaciones del Embarazo/fisiopatología , Teléfono , Adulto , Asma/terapia , Femenino , Humanos , Recuerdo Mental , Embarazo , Complicaciones del Embarazo/terapia , Estudios Retrospectivos , Factores SocioeconómicosRESUMEN
Precise control over the morphology and dimensions of block copolymer (BCP) micelles has attracted interest due to the potential of this approach to generate functional nanostructures. Incorporation of liquid crystalline (LC) block can provide additional ways to vary micellar morphologies, but the formation of uniform micelles with controllable dimensions from LC BCPs has not yet been realized. Herein, we report the preparation of monodisperse cylindrical micelles with a LC poly(2-(perfluorooctyl)ethyl methacrylate (PFMA) core via a fragmentation-thermal annealing (F-TA) process, resembling the "self-seeding" process of crystalline BCP micelles. The average length of the cylinders increases with annealing temperature, with a narrow length distribution (Lw /Ln <1.1). We also demonstrate the potential application of the cylinders with LC cores as a cargo-carrier by the successful incorporation of a hydrophobic fluorescent dye tagged with a fluorooctyl group.
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Refined TiCl4 is the key procedure in producing titanium sponge. Besides, the content of carbon and oxygen (C and O) impurities in titanium sponge and that of C and O impurities in refined TiCl4 presents the 4-times enrichment relationship. Therefore, the content control of the C and O impurities in refined TiCl4 becomes the key part for the quality control of titanium material. In order to control the oxygen and carbon, there is the need to analyze the source of C and O impurities so that strict control can be conducted over the impurities of refined TiCl4. Determination of CO2 in refined TiCl4 was significant for analysis of its impurities. CO2 could be determined by infrared spectroscopy due to its infrared characteristic spectrum line. However, normal infrared absorption cell was not fit for the sample analysis, because TiCl4 easily reacted with moisture in the air and immediately was hydrolyzed to form highly corrosive hydrochloric acid smoke. According to Lambert-Beer Law, which means the concentration (c(ξ)) and absorbance(A) - length (L) curve's slope have direct ratio. The infrared absorption cell with the window film of ZnSe (φ10 mm x 1 mm, wavenumers: 7 800 -440 cm(-1)) and the glass cell (optical path: 42, 22, 12, 7 and 4 mm) was assembled and utilized in determination of the CO2 in refined TiCl4 by standard addition method. The detection limit of CO2 was 0.92 mg x kg(-1), the regression equation was Y = 0.031 1X, R = 0.997 2; With standard addition method, the regression equation of CO2 was Y = 0.131 7X, R = 0.998 6, it's good in linearity relation, the CO2 content in refined TiCl4 is determined to be 1.53 mg x kg(-1) and SD up to 0.04 x mg x kg(-1). RSD of the method precision is between 0.53%-1.27%, while recovery rate is between 89.2%-96.8%. This infrared absorption device was safe, simple and convenient, easily removable and washable, and re-useable. The method could conduct the quantitative analysis over the CO2 content in refined TiCl4 through adding standard sample for one time, it could meet the requirement of determination of CO2 in refined TiCl4.
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The content control of the impurities in refined TiCl4 becomes the key part for the quality control of titanium material. Refined TiCl4 is the key procedure in producing titanium sponge. Besides, the content of the impurities in titanium sponge and that of the impurities in refined TiCl4 presents the 4-times enrichment relationship. Therefore, control the content of the oxygen, there is the need to analyze the source of oxygen impurities so that strict control can be conducted over the impurities of refined TiCl4. Determination of TiOCl2 in refined TiCl4 was significant for analysis of its impurities. TiOCl2 could be determined by infrared spectroscopy due to its infrared characteristic spectrum line. However, normal infrared absorption cell was not fit for the sample analysis, because TiCl4 easily reacted with moisture in the air and immediately was hydrolyzed to form highly corrosive hydrochloric acid smoke. According to Lambert-Beer Law, which means the concentration (c(x)) and absorbance (A)-length (L) curve's slope have direct ratio. The infrared absorption cell with the window film of ZnSe (Φ10 x 1 mm, wavenumers: 7800-440 cm⻹) and the glass cell (optical path: 22, 12, 7 and 4 mm) was assembled and utilized in determination of the TiOCl2 in refined TiCl4 by standard addition method. The detection limit of TiOCl2 was 17.8 mg · kg⻹, the regression equation was Y = 1.011 8X, R = 0.9963; With standard addition method, the regression equation of TiOCl2 was Y = 1.940 0X, R = 0.997 0, it' s good in linearity relation, the TiOCl2 content in refined TiCl4 is determined to be 833.8 mg · kg⻹ and SD up to 40.0 mg · kg⻹. RSD of the method precision is between 0.95%-1.94%, while recovery rate is between 88.5%-93.1%. This infrared absorption device was safe, simple and convenient, easily removable and washable, and re-useable. The method could conduct the quantitative analysis over the TiOCl2 content in refined TiCl4 through adding standard sample for one time, it could meet the requirement of determination of TiOCl2 in refined TiCl4.
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Glycidyl azide polymer energetic thermoplastic elastomer (GAP-ETPE) has become a research hotspot due to its excellent comprehensive performance. In this paper, metastable intermolecular energetic nanocomposites (MICs) were prepared by a simple and safe method, and the catalytic performance for decomposition of GAP-ETPE was studied. An X-ray diffraction (XRD) analysis showed that the MICs exhibited specific crystal formation, which proved that the MICs were successfully prepared. Morphology, surface area, and pore structure analysis showed that the Al/copper ferrite and Al/Fe2O3 MICs had a large specific surface area mesoporous structure. The Al/CuO MICs did not have a mesoporous structure or a large surface area. The structure of MICs led to their different performance for the GAP-ETPE decomposition catalysis. The increase in specific surface area is a benefit of the catalytic performance. Due to the easier formation of complexes, MICs containing Cu have better catalytic performance for GAP-ETPE decomposition than those containing Fe. The conclusions of this study can provide a basis for the adjustment of the catalytic performance of MICs in GAP-ETPE propellants.
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The relatively poor mechanical properties of extruded modified double base (EMDB) propellants limit their range of applications. To overcome these drawbacks, a novel method was proposed to introduce glycidyl azide polymer-based energetic thermoplastic elastomers (GAP-ETPE) with bonding groups into the propellant adhesive. The influence of the molecular structure of three kinds of elastomers on the mechanical properties of the resultant propellant was analyzed. It was found that the mechanical properties of the propellant with 3% CBA-ETPE (a type of GAP-ETPE that features chain extensions using N-(2-Cyanoethyl) diethanolamine and 1,4-butanediol) were improved at both 50 °C and -40 °C compared to a control propellant without GAP-ETPE. The elongation and impact strength of the propellant at -40 °C were 7.49% and 6.58 MPa, respectively, while the impact strength and maximum tensile strength of the propellant at 50 °C reached 21.1 MPa and 1.19 MPa, respectively. In addition, all three types of GAP-ETPE improved the safety of EMDB propellants. The friction sensitivity of the propellant with 3% CBA-ETPE was found to be 0%, and its characteristic drop height H50 was found to be 39.0 cm; 126% higher than the traditional EMDB propellant. These results provide guidance for studies aiming to optimize the performance of EMDB propellants.
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Solution-state self-assemblies of block copolymers to form nanostructures are tremendously attractive for their tailorable morphologies and functionalities. While incorporating moieties with strong ordering effects may introduce highly orientational control over the molecular packing and dictate assembly behaviors, subtle and delicate driving forces can yield slower kinetics to reveal manifold metastable morphologies. Herein, we report the unusually convoluted self-assembly behaviors of a liquid crystalline block copolymer bearing triphenylene discotic mesogens. They undergo unusual multiple morphological transitions spontaneously, driven by their intrinsic subtle liquid crystalline ordering effect. Meanwhile, liquid crystalline orderedness can also be built very quickly by doping the mesogens with small-molecule dopants, and the morphological transitions are dramatically accelerated and various exotic micelles are produced. Surprisingly, with high doping levels, the self-assembly mechanism of this block copolymer is completely changed from intramolecular chain shuffling and rearrangement to nucleation-growth mode, based on which self-seeding experiments can be conducted to produce highly uniform fibrils.
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Glycidyl azide polymer (GAP)-based polyurethane is an ideal elastomeric matrix for high-energy, low-smoke, and insensitive solid propellants. As the skeleton structure of GAP propellants, changes in the structure and properties of GAP elastomers during aging lead to the deterioration of propellant performance (especially in relation to mechanical properties), which causes safety risks. A high-temperature-accelerated aging experiment (70 °C) on a GAP elastomer was conducted. The evolution of the microstructure of the GAP elastomer system was analyzed by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and variations in the macroscopic properties were analyzed by the hardness test and the uniaxial tensile test. The experimental results showed that thermal aging of the GAP elastomer is a coupled process of multiple chemical reactions. The azide groups, urethane groups, and ether bonds were the weak links in the network structure, breaking during the aging process, and the crosslinking density rose and then decreased. Macroscopic properties also showed segmented changes. The aging process was divided into three stages: post-curing (stage one); when the crosslinked network began to break (stage two), and when the crosslinked network was destroyed (stage three). Changes in the microstructure and macroscopic properties were consistent. This work is of great significance for exploring the aging mechanism of GAP propellants and extending their storage life.
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In the title mol-ecule, C26H17N3O2, both indole ring systems are essentially planar, with maximum deviations of 0.019â (2) and 0.033â (1)â Å for the N atoms, and form dihedral angles of 34.40â (9) and 45.06â (8)° with the essentially planar pyrrole ring [maximum deviation = 0.020â (2)â Å]. The dihedral angle between the two indole ring systems is 58.78â (6)°. In the crystal, mol-ecules are connected by pairs of N-Hâ¯O hydrogen bonds, forming inversion dimers and generating R 2 (2)(8) rings. Weak π-π stacking inter-actions, with a centroid-centroid distance of 3.983â (2)â Å, are also observed.