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The property of being stubborn and degradation resistant makes nanoplastic (NP) pollution a long-standing remaining challenge. Here, we apply a designed top-down strategy to leverage the natural hierarchical structure of waste crayfish shells with exposed functional groups for efficient NP capture. The crayfish shell-based organic skeleton with improved flexibility, strength (14.37 to 60.13 MPa), and toughness (24.61 to 278.98 MJ m-3) was prepared by purposefully removing the inorganic components of crayfish shells through a simple two-step acid-alkali treatment. Due to the activated functional groups (e.g., -NH2, -CONH-, and -OH) and ordered architectures with macropores and nanofibers, this porous crayfish shell exhibited effective removal capability of NPs (72.92 mg g-1) by physical interception and hydrogen bond/electrostatic interactions. Moreover, the sustainability and stability of this porous crayfish shell were demonstrated by the maintained high-capture performance after five cycles. Finally, we provided a postprocessing approach that could convert both porous crayfish shell and NPs into a tough flat sheet. Thus, our feasible top-down engineering strategy combined with promising posttreatment is a powerful contender for a recycling approach with broad application scenarios and clear economic advantages for simultaneously addressing both waste biomass and NP pollutants.

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In the biomedical fields of bone regenerative therapy, the immobilization of proteins on the bioceramic particles to maintain their highly ordered structures is significantly important. In this review, we comprehensively discussed the importance of the specific surface layer, which can be called "non-apatitic layer", affecting the immobilization of proteins on particles such as hydroxyapatite and amorphous silica. It was suggested that the water molecules and ions contained in the non-apatitic layer can determine and control the protein immobilization states. In amorphous silica particles, the direct interactions between proteins and silanol groups make it difficult to immobilize the proteins and maintain their highly ordered structures. Thus, the importance of the formation of a surface layer consisting of water molecules and ions (i.e., a non-apatitic layer) on the particle surfaces for immobilizing proteins and maintaining their highly ordered structures was suggested and described. In particular, chlorine-containing amorphous silica particles were also described, which can effectively form the surface layer of protein immobilization carriers. The design of the bio-interactive and bio-compatible surfaces for protein immobilization while maintaining the highly ordered structures will improve cell adhesion and tissue formation, thereby contributing to the construction of social infrastructures to support super-aged society.

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Doping is a crucial strategy to enhance the performance of various organic electronic devices. However, in many cases, the random distribution of dopants in conjugated polymers leads to the disruption of the polymer microstructure, severely constraining the achievable performance of electronic devices. Here, it is shown that by ion-exchange doping polythiophene-based P[(3HT)1-x-stat-(T)x] (x = 0 (P1), 0.12 (P2), 0.24 (P3), and 0.36 (P4)), remarkably high electrical conductivity of >400 S cm-1 and power factor of >16 µW m-1 K-2 are achieved for the random copolymer P3, ranking it among highest ever reported for unaligned P3HT-based films, significantly higher than that of P1 (<40 S cm-1, <4 µW m-1 K-2). Although both polymers exhibit comparable field-effect transistor hole mobilities of ≈0.1 cm2 V-1 s-1 in the pristine state, after doping, Hall effect measurements indicate that P3 exhibits a large Hall mobility up to 1.2 cm2 V-1 s-1, significantly outperforming that of P1 (0.06 cm2 V-1 s-1). GIWAXS measurement determines that the in-plane π-π stacking distance of doped P3 is 3.44 Å, distinctly shorter than that of doped P1 (3.68 Å). These findings contribute to resolving the long-standing dopant-induced-disorder issues in P3HT and serve as an example for achieving fast charge transport in highly doped polymers for efficient electronics.

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Flexible capacitive tactile sensors show great promise in personalized healthcare monitoring and human-machine interfaces, but their practical application is normally hindered because they rarely possess the required comprehensive performance, that is, high pressure sensitivity and fast response within a broad pressure range, high structure robustness, performance consistency, etc. This paper aims to engineer flexible capacitive pressure sensors with highly ordered porous dielectric microstructures and a 3D-printing-based fully solution-processable fabrication process. The proposed dielectric layer with uniformly distributed interior microporous can not only increase its compressibility and dynamic response within an extended pressure range but also enlarge its contact area with electrodes, contributing to a simultaneous improvement in the sensitivity, response speed, detection range, and structure robustness. Meanwhile, owing to its superior abilities in complex structure manufacturing and dimension controlling, the proposed 3D-printing-based fabrication process enables the consistent fabrication of the porous microstructure and thus guarantees device consistency. As a result, the prepared pressure sensors exhibit a high sensitivity of 0.21 kPa-1, fast response and relaxation times of 112 and 152 ms, an interface bonding strength of more than 455.2 kPa, and excellent performance consistency (≤5.47% deviation among different batches of sensors) and tunability. Encouraged by this, the pressure sensor is further integrated with a wireless readout circuit and realizes wireless wearable monitoring of various biosignals (pulse waves and heart rate) and body movements (from slight finger touch to large knee bending). Finally, the influence law of the feature parameters of the porous microstructure on device performance is established by the finite element method, paving the way for sensor optimization. This study motivates the development of flexible capacitive pressure sensors toward practical application.

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Highly ordered superstructures of nanomaterials can be synthesized using protein cages as templates for the assembly of inorganic nanoparticles. Here, we describe in detail the creation of these biohybrid materials. The approach involves computational redesign of ferritin cages, followed by recombinant protein production and purification of the new variants. Metal oxide nanoparticles are synthesized inside the surface-charged variants. The composites are assembled using protein crystallization to yield highly ordered superlattices, which are characterized, for example, with small angle X-ray scattering. This protocol provides a detailed and comprehensive account on our newly established strategy for the synthesis of crystalline biohybrid materials.

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Metal-organic frameworks (MOFs) are proved to be good precursors to derive various nanomaterials with desirable functions, but so far the controllable synthesis of ordered mesoporous derivatives from MOFs has not been achieved. Herein, this work reports, for the first time, the construction of MOF-derived ordered mesoporous (OM) derivatives by developing a facile mesopore-inherited pyrolysis-oxidation strategy. This work demonstrates a particularly elegant example of this strategy, which involves the mesopore-inherited pyrolysis of OM-CeMOF into a OM-CeO2 @C composite, followed by the oxidation removal of its residual carbon, affording the corresponding OM-CeO2 . Furthermore, the good tunability of MOFs helps to allodially introduce zirconium into OM-CeO2 to regulate its acid-base property, thus boosting its catalytic activity for CO2 fixation. Impressively, the optimized Zr-doped OM-CeO2 can achieve above 16 times higher catalytic activity than its solid CeO2 counterpart, representing the first metal oxide-based catalyst to realize the complete cycloaddition of epichlorohydrin with CO2 under ambient temperature and pressure. This study not only develops a new MOF-based platform for enriching the family of ordered mesoporous nanomaterials, but also demonstrates an ambient catalytic system for CO2 fixation.

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The review summarizes the fabrication, microstructures, and sensor applications of highly ordered electrospun nanofibers. In the traditional electrospinning process, electrospun nanofibers usually have disordered or random microstructures due to the chaotic oscillation of the electrospinning jet. Different electrospinning methods can be formed by introducing external forces, such as magnetic, electric, or mechanical forces, and ordered nanofibers can be collected. The microstructures of highly ordered nanofibers can be divided into three categories: uniaxially ordered nanofibers, biaxially ordered nanofibers and ordered scaffolds. The three microstructures are each characterized by being ordered in different dimensions. The regulation and control of the ordered microstructures can promote electrospun nanofibers' mechanical and dielectric strength, surface area and chemical properties. Highly ordered electrospun nanofibers have more comprehensive applications than disordered nanofibers do in effect transistors, gas sensors, reinforced composite materials and tissue engineering. This review also intensively summarizes the applications of highly ordered nanofibers in the sensor field, such as pressure sensors, humidity sensors, strain sensors, gas sensors, and biosensors.

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Highly ordered and uniformly porous structure of conductive foams is a vital issue for various functional purposes such as piezoresistive sensing and electromagnetic interference (EMI) shielding. With the aids of Kevlar polyanionic chains, thermoplastic polyurethane (TPU) foams reinforced by aramid nanofibers (ANF) with adjustable pore-size distribution were successfully obtained via a non-solvent-induced phase separation. In this regard, the most outstanding result is the in situ formation of ANF in TPU foams after protonation of Kevlar polyanion during the NIPS process. Furthermore, in situ growth of copper nanoparticles (Cu NPs) on TPU/ANF foams was performed according to the electroless deposition by using the tiny amount of pre-blended Ti3C2Tx MXene as reducing agents. Particularly, the existence of Cu NPs layers significantly promoted the storage modulus in 2,932% increments, and the well-designed TPU/ANF/Ti3C2Tx MXene (PAM-Cu) composite foams showed distinguished compressive cycle stability. Taking virtues of the highly ordered and elastic porous architectures, the PAM-Cu foams were utilized as piezoresistive sensor exhibiting board compressive interval of 0-344.5 kPa (50% strain) with good sensitivity at 0.46 kPa-1. Meanwhile, the PAM-Cu foams displayed remarkable EMI shielding effectiveness at 79.09 dB in X band. This work provides an ideal strategy to fabricate highly ordered TPU foams with outstanding elastic recovery and excellent EMI shielding performance, which can be used as a promising candidate in integration of satisfactory piezoresistive sensor and EMI shielding applications for human-machine interfaces.

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The self-standing graphene membranes are considered as ideal electrode materials for supercapacitors. However, maintaining highly regularized and uniform graphene membranes with satisfied electrochemical performance is still a challenge. Herein, with the chelation of metal cation and the radial shear force introduced by high-speed spinning, the uniform interlayer channels and shrunken cracks between adjacent nanosheets can be achieved in the metal-intercalated graphene oxide (GO) membranes, thus realizing regularization both in normal and radial direction. With the promotion in electron transfer and electrolyte penetration, the iron cross-linked GO membrane with spin coating for 40 cycles exhibits a high specific capacitance (427 F g-1 at 1 A g-1) and rate capability (42.6% capacitance retention from 1 to 40 A g-1), as well as excellent cyclic capability (90.5% capacitance retention after 20,000 cycles). Particularly, a 21% increasement in capacitance can be achieved after high-speed spinning treatment. Moreover, the spin regularization strategy can be extended to GO membranes cross-linked by various multi-valence metal cations, the electrochemical performance of metal-cation cross-linked GO membrane electrodes after high-speed spinning treatment can also be improved obviously. Therefore, this paper provides a novel method to fabricate highly ordered GO membranes with promising electrochemical performance, which presents an immense potential application in membrane materials applied in energy storage, separation and catalysis.

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Engineered cardiac tissues (ECTs) derived from human induced pluripotent stem cells (hiPSCs) are viable alternatives for cardiac repair, patient-specific disease modeling, and drug discovery. However, the immature state of ECTs limits their clinical utility. The microenvironment fabricated using 3D scaffolds can affect cell fate, and is crucial for the maturation of ECTs. Herein, the authors demonstrate an electric-field-driven (EFD) printed 3D highly ordered microstructure with cell feature size to promote the maturation of ECTs. The simulation and experimental results demonstrate that the EFD jet microscale 3D printing overcomes the jet repulsion without any prior requirements for both conductive and insulating substrates. Furthermore, the 3D highly ordered microstructures with a fiber diameter of 10-20 µm and spacing of 60-80 µm have been fabricated by maintaining a vertical jet, achieving the largest ratio of fiber diameter/spacing of 0.29. The hiPSCs-derived cardiomyocytes formed ordered ECTs with their sarcomere growth along the fiber and developed synchronous functional ECTs inside the 3D-printed scaffold with matured calcium handling compared to the 2D coverslip. Therefore, the EFD jet 3D microscale printing process facilitates the fabrication of scaffolds providing a suitable microenvironment to promote the maturation of ECTs, thereby showing great potential for cardiac tissue engineering.

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A surface-enhanced Raman scattering (SERS)/electrochemical dual-signal readout immunosensor was developed for simultaneous detection of ß-adrenergic agonists salbutamol (SAL), ractopamine (RAC) and phenylethanolamine A (PA). The highly-ordered gold/silver bimetallic cavity array (BMCA) was prepared by electrodepositing Au/Ag nanoparticles to the interstice of highly ordered close-packed polystyrene templates. After electrochemical and SERS characterization, the BMCA was used as the substrate for constructing SERS/electrochemical dual-signal readout immunosensor. 3,3',5,5'-tetramethylbenzidine (TMB), methylene blue (MB) and Nile blue (NB) were selected as the dual-signal reporters, and hybridization chain reaction (HCR) was used as the signal amplifier. The immunoprobe was prepared by absorption of the antibody (Ab) and constructing HCR system embedded with electro/SERS reporter on Au nanoparticles (NPs). After competitive immuno-reaction between coating antigen and analyte for limited Ab on immunoprobe, the SERS/electrochemical dual-signals on BMCA were measured for quantitatively detecting SAL, RAC and PA simultaneously. SAL, RAC and PA were detected in concentration range of 1 pg mL-1 to 100 ng mL-1 with LOD of 0.8, 0.4, and 1.3 pg mL-1, respectively. The applicability of the proposed immunosensor in spiked pork liver samples was verified by the recovery of 95.0%-108.5% with RSD of 6.9%-10.7%. It was proven that the immunosensor was able to detect multiple ß-adrenergic agonists with high sensitivity, specificity, accuracy and precision. The immunosensor can be used as a platform for the determination of other small molecular compounds in biological, food and environmental analytical fields.

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Here, we report the marine degradability of polymers with highly ordered structures in natural environmental water using microbial degradation and biochemical oxygen demand (BOD) tests. Three types of elastic fibers (non-porous as-spun, non-porous drawn, and porous drawn) with different highly ordered structures were prepared using poly[(R)-3-hydroxybutyrate-co-16 mol%-4-hydroxybutyrate] [P(3HB-co-16 mol%-4HB)], a well-known polyhydroxyalkanoate. Scanning electron microscopy (SEM) images indicated that microorganisms attached to the fiber surface within several days of testing and degraded the fiber without causing physical disintegration. The results of BOD tests revealed that more than 80% of P(3HB-co-16 mol%-4HB) was degraded by microorganisms in the ocean. The plastisphere was composed of a wide variety of microorganisms, and the microorganisms accumulated on the fiber surfaces differed from those in the biofilms. The microbial degradation rate increased as the degree of molecular orientation and porosity of the fiber increased: as-spun fiber < non-porous drawn fiber < porous drawn fiber. The drawing process induced significant changes in the highly ordered structure of the fiber, such as molecular orientation and porosity, without affecting the crystallinity. The results of SEM observations and X-ray measurements indicated that drawing the fibers oriented the amorphous chains, which promoted enzymatic degradation by microorganisms.

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The unclear Li2O2 distribution inside an air electrode stems from the difficulty of conducting observation techniques inside a porous electrode. In this work, an integrated air electrode is prepared with highly ordered channels. The morphological composition and distribution of Li2O2 inside the real air electrode are clearly observed for the first time. The results show that the toroidal Li2O2 is constrained by the channel size and exhibits a larger diameter on the separator side at high currents. In contrast to the reported single-factor experiments, the coupling effects of charge transfer impedance and concentration polarization on sudden death are analyzed in-depth at low and high currents. The growth model suggests that toroidal Li2O2 exhibits a high dependence on the electrode surface structure. A new route is proposed in which the Li2O2/electrode interface of a toroid is controlled partially by the second single-electron reduction.

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Cardiac microphysiological systems are accurate in vitro platforms that reveal the biological mechanisms underlying cardiopathy, accelerating pharmaceutical research in this field. Current cardiac microphysiological devices and organs-on-chips consist of several layers prepared with complex, multi-step processes. Incorporating inorganic photonic crystals may cause long-term biocompatibility issues. Herein, micropatterned hydrogels with anisotropic structural colors are prepared by locking shear-oriented tunicate cellulose nanocrystals (TCNCs) in hydrogel networks through in situ polymerization, allowing the visualization and monitoring of cardiomyocytes. The anisotropic hydrogels are composed of highly ordered TCNCs with bright interference color and micro-grooved methacrylated gelatin with excellent biocompatibility. The microgroove patterns induce cardiomyocyte alignment and the autonomous beating of cardiomyocytes causes the hydrogels to deform, dynamically shifting the interference color. These micropatterned hydrogels could noninvasively monitor real-time changes of cardiomyocytes under pharmaceutical treatment and electrical stimulation through wavelength shifts in the transmittance spectra. This system provides a new way to detect the beat rate of cardiac tissue and it may contribute to high throughput develop.

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Moisture-trigged electricity generator (MEG) that can convert ubiquitous moisture into electricity are highly desirable for developing renewable energy supply and ameliorating the crisis in energy. Constructing an asymmetric ordered, namely gradient ordered porous membrane has great potential in MEG. Herein, a series of cellulose acetate (CA)-based membranes with ordered asymmetric honeycomb membranes were fabricated by Breath Figure method, along with silver nanowires (AgNWs) coating. The asymmetric gradient honeycomb pores were achieved by graft modification of lauroyl chloride and adjustment of relative humidity, which not only endowed the MEG with sensitive sensing signals transport under tension and humidity fluctuations but also enhanced voltages generation speed under flowing moisture. The current study provides a facile and scalable strategy for constructing asymmetric gradient ordered porous materials and creates more possibilities for MEG self-powered flexible wearable electronic devices.

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The thermophysical properties at the nanoscale are key characteristics that determine the operation of nanoscale devices. Additionally, it is important to measure and verify the thermal transfer characteristics with a few nanometer or atomic-scale resolutions, as the nanomaterial research field has expanded with respect to the development of molecular and atomic-scale devices. Scanning thermal microscopy (SThM) is a well-known method for measuring the thermal transfer phenomena with the highest spatial resolution. However, considering the rapid development of atomic materials, the development of an ultra-sensitive SThM for measuring pico-watt (pW) level heat transfer is essential. In this study, to measure molecular- and atomic-scale phenomena, a pico-watt scanning thermal microscopy (pW-SThM) equipped with a calorimeter capable of measuring heat at the pW level was developed. The heat resolution of the pW-SThM was verified through an evaluation experiment, and it was confirmed that the temperature of the metal line heater sample could be quantitatively measured by using the pW-SThM. Finally, we demonstrated that pW-SThM detects ultra-small differences of local heat transfer that may arise due to differences in van der Waals interactions between the graphene sheets in highly ordered pyrolytic graphite. The pW-SThM probe is expected to significantly contribute to the discovery of new heat and energy transfer phenomena in nanodevices and two-dimensional materials that have been inaccessible through experiments.

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Developing photocatalysts that are inexpensive and efficient in degrading pollutants are essential for environmental remediation. Herein, a novel system of perylene diimide (PDI)/CuS p-n heterojunction was synthesized by a two-step self-assembly strategy for removal of tetracycline in waste water. Results showed that PDI/CuS-10% exhibited highest photocatalytic behavior. The apparent rate constants for tetracycline (TC) degradation for the blend were 5.27 and 2.68 times higher than that of CuS or PDI, respectively. The enhancement of photocatalytic activity was mainly attributed to the π-π stacking and p-n junction, which can accelerate the separation of the photo-generated h+-e- pairs. Besides, the light absorption of PDI/CuS from 800 to 200 nm was significantly enhanced and the absorption edge even reached the near-infrared region, which also played an important role in providing desired photocatalytic properties. Surprisingly, PDI/CuS could maintain high catalytic activity even after 5 cycles under simulated conditions, indicating that the composite had high potential for practical applications. Owing to high efficiency, low cost and wide application range, the PDI/CuS nanocomposites are promising candidates for environmental remediation.

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2D carbon nitride nanosheets have attracted ever-increasing interest in photocatalysis due to their unique structural advantages. However, the nanosheets synthesized by the traditional methods, such as post oxidation and liquid exfoliation, have suffered from in-plane disorder with abundant structural defects, which seriously counteracts their structural benefits for photocatalysis. Herein, it is demonstrated that polymer carbon nitride nanosheets with in-plane highly ordered structure (PCNNs-IHO) can be successfully prepared by on-surface polymerization of melamine on NaCl crystal surface at elevated temperatures. The NaCl crystals with relative high surface energy not only facilitate the adsorption and activation of melamine to undergo condensation reaction, but also function as unique substrates to orientate the assembly of 2D nanosheet structure. In addition, NaCl also acts as a reactant to provide Na+ doping into carbon nitride matrix, affording PCNNs-IHO with robust structural base sites. Benefiting from this structural basicity, PCNNs-IHO exhibits superior photocatalytic performance toward CH3 SH mineralization under visible light irradiation.

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As the power density and integration level of electronic devices increase, there are growing demands to improve the thermal conductivity of polymers for addressing the thermal management issues. On the basis of the ultrahigh intrinsic thermal conductivity, graphene has exhibited great potential as reinforcing fillers to develop polymer composites, but the resultant thermal conductivity of reported graphene-based composites is still limited. Here, an interconnected and highly ordered graphene framework (HOGF) composed of high-quality and horizontally aligned graphene sheets was developed by a porous film-templated assembly strategy, followed by a stress-induced orientation process and graphitization post-treatment. After embedding into the epoxy (EP), the HOGF/EP composite (24.7 vol %) exhibits a record-high in-plane thermal conductivity of 117 W m-1 K-1, equivalent to ≈616 times higher than that of neat epoxy. This thermal conductivity enhancement is mainly because the HOGF as a filler concurrently has high intrinsic thermal conductivity, relatively high density, and a highly ordered structure, constructing superefficient phonon transport paths in the epoxy matrix. Additionally, the use of our HOGF/EP as a heat dissipation plate was demonstrated, and it achieved 75% enhancement in practical thermal management performance compared to that of conventional alumina for cooling the high-power LED.

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Polydimethylsiloxane (PDMS), in spite of its well-defined helical structure, is an amorphous fluid even at extremely high molecular weights. The cause of this behavior is the high flexibility of the siloxane backbone and the lack of intermolecular interactions attributed to the presence of methyl groups. These make PDMS incompatible with almost any organic or inorganic component leading to phase separation in siloxane-siloxane copolymers containing blocks with polar organic groups and in siloxane-organic copolymers, where dimethylsiloxane segments co-exist with organic ones. Self-assembly at the micro- or nanometric scale is common in certain mixed structures, including micelles, vesicles, et cetera, manifesting reversibly in response to an external stimulus. Polymers with a very high degree of ordering in the form of high-quality crystals were obtained when siloxane/silane segments co-exist with coordinated metal blocks in the polymer chain. While in the case of coordination of secondary building units (SBUs) with siloxane ligands 1D chains are formed; when coordination is achieved in the presence of a mixture of ligands, siloxane and organic, 2D structures are formed in most cases. The Romanian research group's results regarding these aspects are reviewed: from the synthesis of classic, amorphous silicone products, to their adaptation for use in emerging fields and to new self-assembled or highly ordered structures with properties that create perspectives for the use of silicones in hitherto unexpected areas.