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1.
Polymers (Basel) ; 16(17)2024 Aug 30.
Article in English | MEDLINE | ID: mdl-39274111

ABSTRACT

Mechanical energy harvesters made from soft and flexible materials can be employed as energy sources for wearable and implantable devices. However, considering how human organs and joints expand and bend in many directions, the energy generated in response to a mechanical stimulus in only one direction limits the applicability of mechanical energy harvesters. Here, we report carbon nanotube (CNT) sheets/an elastomer bilayer harvesting electrode (CBHE) that converts two-axis mechanical stimulation into electrical energy. The novel microwinkled structure of the CBHE successfully demonstrates an electrochemical double-layer (EDL) capacitance change from biaxial mechanical stimulation, thereby generating electrical power (0.11 W kg-1). Additionally, the low modulus (0.16 MPa) and high deformability due to the elastomeric substrate suggest that the CBHE can be applied to the human body.

2.
Polymers (Basel) ; 16(17)2024 Sep 01.
Article in English | MEDLINE | ID: mdl-39274129

ABSTRACT

Electro-conductive films with excellent flexibility and thermal behavior have great potential in the fields of wearable electronics, artificial muscle, and soft robotics. Herein, we report a super-elastic and electro-conductive composite film with a sandwich structure. The composite film was constructed by spraying Polyvinyl alcohol (PVA) polymers onto a buckled conductive carbon nanotube-polydimethylsiloxane (CNTs-PDMS) composite film. In this system, the PVA and PDMS provide water sensing and stretchability, while the coiled CNT film offers sufficient conductivity. Notably, the composite film possesses high stretchability (205%), exceptional compression sensing ability, humility sensing ability, and remarkable electrical stability under various deformations. The produced CNT composite film exhibited deformation (bending/twisting) and high electro-heating performance (108 °C) at a low driving voltage of 2 V. The developed CNT composite film, together with its exceptional sensing and electrothermal performance, provides the material with promising prospects for practical applications in wearable electronics.

3.
Article in English | MEDLINE | ID: mdl-39269965

ABSTRACT

Semiconductor single-walled carbon nanotube (s-SWNT) networks have gained prominence in electronic devices due to their cost-effectiveness, relatively production-naturality, and satisfactory performance. Configuration, density, and resistance of SWNT-SWNT junctions are considered crucial factors influencing the overall conductivity of s-SWNT networks. In this study, we present a method for inferring the lower bounds of the SWNT-SWNT junction resistance in s-SWNT networks based on conductive atomic force microscopy TUNA images. This method further enables the proposal of a classification for SWNT-SWNT junctions based on the current behavior relative to their surroundings. The three types of SWNT-SWNT junctions are denoted as (i) true contact (T), (ii) poor contact (P), and (iii) false contact (F). Of them, the true and poor contacts, respectively, represent good and poor electrical contact for the subject SWNT-SWNT junctions whose electrical conductivity hardly improves under external tip pressure, while that of the false contact can be further improved by external pressure. Statistical analysis demonstrates that while T-type junctions make a significant contribution to network conductivity, their proportion accounts for only approximately 40%. The P-type and F-type junctions, which constitute over 60% of the total, may be a contributing factor that constrains the overall conductivity of the s-SWNT networks. The height ratio of the junction to the sum of two SWNTs was also observed to exhibit variations among the three types. Finally, we propose a three-dimensional model to elucidate the formation mechanism underlying each type of junction. The present study provides insights into the performance of spontaneous contacts between s-SWNTs in the networks, and the systematic image acquisition and junction classification processes may provide support for future advancements in these networks.

4.
Article in English | MEDLINE | ID: mdl-39276126

ABSTRACT

The combination of wearable sensors with machine learning enables intelligent perception in human-machine interaction and healthcare, but achieving high sensitivity and a wide working range in flexible strain sensors for signal acquisition and accurate recognition remains challenging. Herein, we introduced carboxymethyl cellulose (CMC) into a carbon nanotubes (CNTs)/MXene hybrid network, forming tight anchoring among the conductive materials and, thus, bringing enhanced interaction. The silicone-rubber-encapsulated CMC-anchored CNTs/MXene (CCM) strain sensor exhibits an excellent sensitivity (maximum gauge factor up to 71 294), wide working range (200%), ultralow detection limit (0.05%), and outstanding durability (over 10 000 cycles), which is superior to most of the recently reported counterparts also based on a conductive composite film. Moreover, the sensor achieves seamless integration with human skin with the help of a poly(acrylic acid) adhesive layer, successfully obtaining stable and clear waveforms with meaningful profiles from the human body. On this basis, we proposed and realized a novel in-air handwriting recognition method via extracting multiple features of high-quality strain signals assisted by deep neural networks, achieving a high classification accuracy of 98.00 and 94.85% for Arabic numerals and letters, respectively. Our work provides an effective approach for significantly improving strain sensing performance, thereby facilitating innovative applications of flexible sensors.

5.
Arch Toxicol ; 2024 Sep 13.
Article in English | MEDLINE | ID: mdl-39269499

ABSTRACT

Fullerene whiskers (FLW)s are thin rod-like structures composed of C60 and C70 fullerene (FL). The shape of FLWs suggests potential toxic effects including carcinogenicity to the lung and pleura, similar to effects elicited by asbestos and multi-walled carbon nanotubes (MWCNT)s. However, no long-term carcinogenic studies of FL or FLW have been conducted. In the present study we investigated the pulmonary and pleural carcinogenicity of FL and FLW. Twelve-week-old male F344 rats were administered 0.25 or 0.5 mg FL, FLW, MWCNT-7, and MWCNT-N by intra-tracheal intra-pulmonary spraying (TIPS). Acute lung lesions and carcinogenicity were analyzed at 1 and 104 weeks after 8 doses/15 days TIPS administration. At week 1, FLW, MWCNT-7, and MWCNT-N significantly increased alveolar macrophage infiltration. Expression of Ccl2 and Ccl3, reactive oxygen species production, and cell proliferation were significantly increased by administration of MWCNT-7 and MWCNT-N but not FL or FLW. At week 104, the incidence of bronchiolo-alveolar adenoma plus adenocarcinoma was significantly increased in the MWCNT-7 and MWCNT-N groups, and the incidence of mesothelioma was significantly increased in the MWCNT-7 group. No significant induction of pulmonary or pleural tumorigenesis was observed in the FL or FLW groups. The number of 8-OHdG-positive cells in the alveolar epithelium was significantly increased in the MWCNT-7 and MWCNT-N groups but not in the FL or FLW groups. FL and FLW did not exert pulmonary or pleural carcinogenicity in our study. In addition, oxidative DNA damage was implicated in MWCNT-induced lung carcinogenesis, suggesting that it may be a useful initial marker of carcinogenicity.

6.
Small ; : e2406173, 2024 Sep 03.
Article in English | MEDLINE | ID: mdl-39225362

ABSTRACT

Covalent organic frameworks (COFs), featuring structural diversity, permanent porosity, and functional versatility, have emerged as promising electrode materials for rechargeable batteries. To date, amorphous polymer, COF, or their composites are mostly explored in lithium-ion batteries (LIBs), while their research in other alkali metal ion batteries is still in infancy. This can be due to the challenges that arise from large volume changes, slow diffusion kinetics, and inefficient active site utilization by the large Na+ or K+ ion. Herein, microwave-assisted imide-based 2D COF, TAPB-NDA covalently connected with amine-functionalized carbon nanotubes (TAPB-NDA@CNT) targeting the application in both Li-/Na-ion batteries, is synthesized. As-synthesized, TAPB-NDA@CNT50 displays the good performance as LIB cathode with a specific capacity of ≈138 mAh g-1 at 25 mA g-1, long cycling stability (81.2% retention after 2000 cycles at 300 mA g-1), with excellent reversible capacity retention of ≈79.6%. Similarly, TAPB-NDA@CNT50, when employed in sodium-ion battery (SIB), exhibited 136.7 mAh g-1 specific capacity at 25 mA g-1, retained ≈80% of the reversible capacity after 1000 cycles at 300 mA g-1 and showing excellent rate performance. The structural advantage of TAPB-NDA@CNT will encourage researchers to design COF-based cathodes for the alkali ion batteries.

7.
Adv Mater ; : e2409062, 2024 Sep 06.
Article in English | MEDLINE | ID: mdl-39240064

ABSTRACT

The development of sodium metal batteries has long been impeded by dendrite formation issues. State-of-the-art strategies, exemplified by sodiophilic hosting/seeding layers, have demonstrated great success in suppressing dendrite formation. However, addressing high-capacity applications (>10 mAh cm-2) remains a significant challenge. Herein, the study revisits the interlayer strategy by simply covering a carbon nanotube (CNT) film onto the surface of a sodium metal anode, unlocking its overlooked potential for ultrahigh capacity applications. In situ Raman spectroscopy reveals the interlayer's fast-ion-storage feature, enabling deposition at the interface without capacity limitations. Consequently, in symmetric cells, one-year long-term reversible cycling and a record-high capacity of 50 mAh cm-2 under 90% depth of discharge is achieved, representing a significant breakthrough for stabilizing Na anode. Furthermore, the full cell with a 50-µm thin metal anode and a high-loading Na3V2(PO4)3 cathode (12 mg cm-2) delivers a stable capacity of 94 mAh g-1 for 270 cycles (94% capacity retention).

8.
Adv Sci (Weinh) ; : e2402916, 2024 Sep 03.
Article in English | MEDLINE | ID: mdl-39226210

ABSTRACT

The electrochemical splitting of water for hydrogen production faces a major challenge due to its anodic oxygen evolution reaction (OER), necessitating research on the rational design and facile synthesis of OER catalysts to enhance catalytic activity and stability. This study proposes a ligand-induced MOF-on-MOF approach to fabricate various trimetallic MnFeCo-based Prussian blue analog (PBA) nanostructures. The addition of [Fe(CN)6]3- transforms them from cuboids with protruding corners (MnFeCoPBA-I) to core-shell configurations (MnFeCoPBA-II), and finally to hollow structures (MnFeCoPBA-III). After pyrolysis at 800 °C, they are converted into corresponding PBA-derived carbon nanomaterials, featuring uniformly dispersed Mn2Co2C nanoparticles. A comparative analysis demonstrates that the Fe addition enhances catalytic activity, while Mn-doped materials exhibit excellent stability. Specifically, the optimized MnFeCoNC-I-800 demonstrates outstanding OER performance in 1.0 m KOH solution, with an overpotential of 318 mV at 10 mA cm-2, maintaining stability for up to 150 h. Theoretical calculations elucidate synergistic interactions between Fe dopants and the Mn2Co2C matrix, reducing barriers for oxygen intermediates and improving intrinsic OER activity. These findings offer valuable insights into the structure-morphology relationships of MOF precursors, advancing the development of highly active and stable MOF-derived OER catalysts for practical applications.

9.
Materials (Basel) ; 17(15)2024 Jul 25.
Article in English | MEDLINE | ID: mdl-39124340

ABSTRACT

The measurement of the electronic bandgap and exciton binding energy in quasi-one-dimensional materials such as carbon nanotubes is challenging due to many-body effects and strong electron-electron interactions. Unlike bulk semiconductors, where the electronic bandgap is well known, the optical resonance in low-dimensional semiconductors is dominated by excitons, making their electronic bandgap more difficult to measure. In this work, we measure the electronic bandgap of networks of polymer-wrapped semiconducting single-walled carbon nanotubes (s-SWCNTs) using non-ideal p-n diodes. We show that our s-SWCNT networks have a short minority carrier lifetime due to the presence of interface trap states, making the diodes non-ideal. We use the generation and recombination leakage currents from these non-ideal diodes to measure the electronic bandgap and excitonic levels of different polymer-wrapped s-SWCNTs with varying diameters: arc discharge (~1.55 nm), (7,5) (0.83 nm), and (6,5) (0.76 nm). Our values are consistent with theoretical predictions, providing insight into the fundamental properties of networks of s-SWCNTs. The techniques outlined here demonstrate a robust strategy that can be applied to measuring the electronic bandgaps and exciton binding energies of a broad variety of nanoscale and quantum-confined semiconductors, including the most modern nanoscale transistors that rely on nanowire geometries.

10.
Nanomaterials (Basel) ; 14(15)2024 Jul 28.
Article in English | MEDLINE | ID: mdl-39120365

ABSTRACT

The carbon nanotube cold cathode has important applications in the X-ray source, microwave tube, neutralizer, etc. In this study, the characteristics of carbon nanotube (CNT) electron gun in series with metal-oxide-semiconductor field-effect transistor (MOSFET) were studied. CNTs were prepared on a stainless steel substrate by chemical vapor deposition and assembled with a mesh gate to form an electron gun. The anode current of the electron gun can be accurately regulated by precisely controlling the MOSFET gate voltage in the subthreshold region from 1 to 40 µA. The current stability measurements show the cathode current fluctuation was 0.87% under 10 h continuous operation, and the corresponding anode current fluctuation was 2.3%. The result has demonstrated that the MOSFET can be applied for the precise control of the CNT electron gun and greatly improve current stability.

11.
Nanomaterials (Basel) ; 14(15)2024 Jul 29.
Article in English | MEDLINE | ID: mdl-39120376

ABSTRACT

In this work, the effect of multi-walled carbon nanotubes (MWCNT1, MWCNT2, and MWCNT3) with different outer diameters and specific surface areas on the mechanical and electrical properties of cement mortar have been investigated. Various concentrations of MWCNTs were used (0.05, 0.10, and 0.15%), the effective dispersion of which was carried out by an Ultrasonic machine (for 40 min with 160 W power and a 24 kHz frequency) using a surfactant. Composites have been processed with a biosilica content of 10% by weight of cement and without it. Compressive strength tests were carried out on days 7 and 28 of curing. The 7-day compressive strength of samples prepared without biosilica increased compared to the result of the control sample (6.4% for MWCNT1, 7.4% for MWCNT2, and 10.8% for MWCNT3), as did those using biosilica (6.7% in the case of MWCNT1, 29.2% for MWCNT2, and 2.1% for MWCNT3). Compressive strength tests of 28-day specimens yielded the following results: 21.7% for MWCNT1, 3.8% for MWCNT2, and 4.2% for MWCNT3 in the absence of biosilica and 8.5%, 12.6%, and 6.3% with biosilica, respectively. The maximum increase in compressive strength was observed in the composites treated with a 0.1% MWCNT concentration, while in the case of 0.05 and 0.15% concentrations, the compressive strengths were relatively low. The MWCNT-reinforced cement matrix obtained electrical properties due to the high electrical conductivity of these particles. The effect of MWCNT concentrations of 0.05, 0.10, and 0.15 wt% on the electrical properties of cement mortar, especially the bulk electrical resistivity and piezoresistive characteristics of cement mortar, was studied in this work. At a concentration of 0.05%, the lowest value of resistivity was obtained, and then it started to increase. The obtained results show that all investigated specimens have piezoresistive properties and that the measurements led to a deviation in fractional change in resistivity.

12.
Nanomaterials (Basel) ; 14(15)2024 Jul 29.
Article in English | MEDLINE | ID: mdl-39120378

ABSTRACT

There is a need for the assessment of respiratory hazard potential and mode of action of carbon nanotubes (CNTs) before their approval for technological or medical applications. In CNT-exposed lungs, both alveolar macrophages (MФs), which phagocytose CNTs, and alveolar epithelial type II cells (AECII cells), which show tissue injury, are impacted but cell-cell interactions between them and the impacted mechanisms are unclear. To investigate this, we first optimized an air-liquid interface (ALI) transwell coculture of human AECII cell line A549 (upper chamber) and human monocyte cell line THP-1 derived macrophages (lower chamber) in a 12-well culture by exposing macrophages to CNTs at varying doses (5-60 ng/well) for 12-48 h and measuring the epithelial response markers for cell differentiation/maturation (proSP-C), proliferation (Ki-67), and inflammation (IL-1ß). In optimal ALI epithelial-macrophage coculture (3:1 ratio), expression of Ki-67 in AECII cells showed dose dependence, peaking at 15 ng/well CNT dose; the Ki-67 and IL-1ß responses were detectable within 12 h, peaking at 24-36 h in a time-course. Using the optimized ALI transwell coculture set up with and without macrophages, we demonstrated that direct interaction between CNTs and MФs, but not a physical cell-cell contact between MФ and AECII cells, was essential for inducing immunotoxicity (proliferative and inflammatory responses) in the AECII cells.

13.
Small ; : e2401735, 2024 Aug 09.
Article in English | MEDLINE | ID: mdl-39126177

ABSTRACT

Lithium-ion batteries (LIBs) are paramount in energy storage in consumer electronics and electric vehicles. However, a narrow operating temperature range severely constrains their evolution. In this study, a wide-temperature operating LIB system is constructed utilizing carbon nanotube (CNT)-based electrodes and a "constructive alliance" electrolyte. The unique microstructure of the CNT current collector, with high electrical and thermal conductivity, accelerates the reaction kinetics of active materials at subzero temperatures and optimizes the thermal management of the entire electrode at elevated temperatures. Furthermore, a strategy employing the "constructive alliance" electrolyte is proposed, demonstrating that a simple combination of commercially available electrolytes can enhance resilience to harsh thermal conditions. Molecular dynamics simulations and density functional theory calculations reveal that the hybrid electrolyte predominantly adopts aggregate solvation structures and possesses low Li+ desolvation barriers regardless of thermal variations. Consequently, the assembled Li4Ti5O12//LiCoO2 full cell, with a negative/positive electrode material ratio of 1.2, exhibits outstanding electrochemical performance in the wide temperature range of -40 and 60 °C. This innovative strategy overcomes challenges in wide-temperature electrolyte research and offers promise for next-generation wide-temperature LIBs.

14.
ACS Nano ; 18(33): 22474-22483, 2024 Aug 20.
Article in English | MEDLINE | ID: mdl-39110064

ABSTRACT

High density and high semiconducting-purity single-walled carbon nanotube array (A-CNT) have recently been demonstrated as promising candidates for high-performance nanoelectronics. Knowledge of the structures and arrangement of CNTs within the arrays and their interfaces to neighboring CNTs, metal contacts, and dielectrics, as the key components of an A-CNT field effect transistor (FET), is essential for device mechanistic understanding and further optimization, particularly considering that the current technologies for the fabrication of A-CNT wafers are mainly laboratory-level solution-based processes. Here, we conduct a systematic investigation into the microstructures of A-CNT FETs mainly via cross-sectional high-resolution transmission electron microscopy and tentatively establish a framework consisting of up to 11 parameters which can be used for structure-side quality evaluation of the A-CNT FETs. The parameter ensemble includes the diameter, length (or terminal), and density distribution of CNTs, radial deformation of CNTs, array alignment defects, surface crystallography facets of contact metal, thickness distribution of high-k dielectrics (HfO2), and the contact ratios for the CNT-CNT, CNT-metal, CNT-dielectric, and CNT-substrate interfaces. Enriched array alignment defects, i.e., bundle, stacking, misorientation, and voids, are observed with a total ratio sometimes up to ∼90% in pristine A-CNTs and even up to ∼95% after the device fabrication process. Thus, they are suggested as the prevalent performance-limiting factors for A-CNT FETs. Complex interfacial structures are observed at the CNT-CNT, CNT-metal contact, and CNT-high-k dielectric interfaces, making the local environment and the property of each component CNT involved in an A-CNT FET distinct from others in terms of the diameters, radial deformation, and interactions with the local surroundings (mainly through van der Waals interactions). The present study suggests further improvements on the fabrication technology of A-CNT wafers and devices and mechanistic investigations into the impacts of complex array alignment defects and interface structures on the electrical performance of A-CNT FETs as well.

15.
Small ; : e2402083, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-39140166

ABSTRACT

Graphyne nanoscrolls (GNSs) have attracted significant research interest because of their wide-ranging applications. However, the production of GNSs via a self-scrolling approach is environment dependent. Here, molecular dynamics simulations are conducted to evaluate the self-scrolling behavior of an α-graphyne (α-GY) ribbon on a carbon nanotube (CNT) within various multiphysical environments, accounting for the interactions among temperature, electric field, and argon gas. The results demonstrate that the fabrication of an α-GNS lies in the interplay of van der Waals (vdW) forces among the components in a vacuum. Notably, the α-GY ribbon is easier to scroll onto a thicker CNT. The electric field attenuates the vdW interaction, necessitating thicker CNTs for successful self-scrolling under a stronger electric field. In argon, both the vdW interaction and nanoscale pore contribute to the overlap formation. At 300 K, increasing argon density prolongs the time required for α-GNS formation, with self-scrolling failing beyond a critical gas density threshold. Moreover, the self-scrolling becomes easier at higher temperatures. In multiphysical environments, the interplay between the electric field and the gas density dictates the self-scrolling at low temperatures. Finally, reasonable suggestions are given for successful self-scrolling. The conclusions offer valuable insights for the practical fabrication of α-GNS.

16.
Angew Chem Int Ed Engl ; : e202404196, 2024 Aug 20.
Article in English | MEDLINE | ID: mdl-39161281

ABSTRACT

In this study, we present a novel plasma-enabled strategy for the rapid breakdown of various types of plastic wastes, including mixtures, into high-value carbon nanomaterials and hydrogen. The H2 yield and selectivity achieved through the catalyst-free plasma-enabled strategy are 14.2 and 5.9 times higher, respectively, compared to those obtained with conventional thermal pyrolysis. It is noteworthy that this catalyst-free plasma alone approach yields a significantly higher energy yield of H2 (gH2/kWh) compared to other pyrolysis processes. By coupling plasma pyrolysis with thermal catalytic process, employing of 1 wt.% M/CeO2 atomically dispersed catalysts can further enhance hydrogen production. Specifically, the 1 wt.% Co/CeO2 catalyst demonstrated excellent catalytic performance throughout the 10 cycles of plastic waste decomposition, achieving the highest H2 yield of 46.7 mmol/gplastic (equivalent to 64.4% of theoretical H2 production) and nearly 100% hydrogen atom recovery efficiency at the 7th cycle. Notably, the H2 yield achieved over the atomically dispersed Fe on CeO2 surface in the integrated plasma-thermal catalytic process is comparable to that obtained with Fe particles on CeO2 surface (10 wt.%). This innovative and straightforward approach provides a promising and expedient strategy for continuously converting diverse plastic waste streams into high-value products conducive to a circular plastic economy.

17.
Sci Rep ; 14(1): 19055, 2024 08 17.
Article in English | MEDLINE | ID: mdl-39154029

ABSTRACT

Beta-tricalcium phosphate (ß-TCP) scaffolds manufactured through the foam replication method are widely employed in bone tissue regeneration. The mechanical strength of these scaffolds is a significant challenge, partly due to the rheological properties of the original suspension. Various strategies have been explored to enhance the mechanical properties. In this research, ß-TCP scaffolds containing varying concentrations (0.25-1.00 wt%) of multi-walled carbon nanotubes (MWCNT) were developed. The findings indicate that the addition of MWCNTs led to a concentration-dependent improvement in the viscosity of ß-TCP suspensions. All the prepared slurries exhibited viscoelastic behavior, with the storage modulus surpassing the loss modulus. The three time interval tests revealed that MWCNT-incorporated ß-TCP suspensions exhibited faster structural recovery compared to pure ß-TCP slurries. Introducing MWCNT modified compressive strength, and the optimal improvement was obtained using 0.75 wt% MWCNT. The in vitro degradation of ß-TCP was also reduced by incorporating MWCNT. While the inclusion of carbon nanotubes had a marginal negative impact on the viability and attachment of MC3T3-E1 cells, the number of viable cells remained above 70% of the control group. Additionally, the results demonstrated that the scaffold increased the expression level of osteocalcin, osteoponthin, and alkaline phosphatase genes of adiposed-derived stem cells; however, higher levels of gene expersion were obtained by using MWCNT. The suitability of MWCNT-modified ß-TCP suspensions for the foam replication method can be assessed by evaluating their rheological behavior, aiding in determining the critical additive concentration necessary for a successful coating process.


Subject(s)
Calcium Phosphates , Nanotubes, Carbon , Tissue Engineering , Tissue Scaffolds , Calcium Phosphates/chemistry , Nanotubes, Carbon/chemistry , Tissue Scaffolds/chemistry , Tissue Engineering/methods , Animals , Mice , Cell Line , Bone and Bones/metabolism , Cell Survival/drug effects , Materials Testing , Bone Regeneration/drug effects , Osteoblasts/metabolism , Osteoblasts/drug effects , Osteoblasts/cytology , Viscosity
18.
Chemphyschem ; : e202400618, 2024 Aug 05.
Article in English | MEDLINE | ID: mdl-39104119

ABSTRACT

Technological advances frequently interface biomolecules with nanomaterials at non-physiological conditions, necessitating response characterization of key processes. Similar encounters are expected in cellular contexts. We report in silico investigations of the response of diverse protein conformational states to lowering of temperature and imposition of spatial constraints. Conformational states are represented by folded form of the Albumin binding domain (ABD) protein, its compact denatured form, and structurally disordered nascent folding elements. Data from extensive simulations are evaluated to elicit structural, thermodynamic and dynamic responses of the states and their associated environment. Analyses reveal alterations to folding propensity with reduced thermal energy and confinement, with signatures of trend reversal in highly disordered states. Across temperatures, confinement has restrictive effects on volume and energetic fluctuations, leading to narrowing of differences in isothermal compressibility (κ) and heat capacities (Cp). While excess (over ideal gas) entropy of the hydration layer marks dependence on the conformational state at bulk, confinement triggers erasure of differences. These observations are largely consistent with timescales of protein-water hydrogen bonding dynamics. The results implicate multi-factorial associations within a simple bio-nano complex. We expect the current study to motivate investigations of more biologically relevant interfaces towards mechanistic understanding and potential applications.

19.
ACS Appl Mater Interfaces ; 16(32): 42343-42351, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-39096308

ABSTRACT

SiOx anode materials are among the most promising candidates for next-generation high-energy-density lithium-ion batteries (LIBs). However, their commercial application is hindered by poor conductivity, low initial Coulombic efficiency (ICE), and an unstable solid electrolyte interface. Developing cost-effective SiOx anodes with high electrochemical performance is crucial for advanced LIBs. To tackle these issues, this study utilized APTES as a silicon source and carbon nanotubes (CNTs) as additives to prepare a T-SiOx/C/CNTs composite material with N doping and in situ carbon coating using a "molecular assembly combined with controlled pyrolysis" strategy under mild conditions. The in situ carbon coating, formed by the pyrolysis of organic groups on the molecular precursor, effectively protects the inner SiOx active material. The introduced CNTs enhance electron migration and improve the rigidity of the carbon coating layer. The prelithiated T-SiOx@C/CNTs electrode achieves an ICE of 91.6%, with a specific capacity of 622 mAh g-1 after 400 cycles at 1 A g-1 and 475.8 mAh g-1 after 800 cycles. Full cell tests with commercial NCM811 cathodes further demonstrate the potential of T-SiOx@C/CNTs as a highly promising anode material. This work provides some insights into the rational design of advanced anode materials for LIBs, paving the way for their future development and application.

20.
Natl Sci Rev ; 11(8): nwae242, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39165665

ABSTRACT

Reproducing the outstanding selectivity achieved by biological ion channels in artificial channel systems can revolutionize applications ranging from membrane filtration to single-molecule sensing technologies, but achieving this goal remains a challenge. Herein, inspired by the selectivity filter structure of the KcsA potassium channel, we propose a design of biomimetic potassium nanochannels by functionalizing the wall of carbon nanotubes with an array of arranged carbonyl oxygen atoms. Our extensive molecular dynamics simulations show that the biomimetic nanochannel exhibits a high K+ permeation rate along with a high K+/Na+ selectivity ratio. The free energy calculations suggest that the low Na+ permeability is the result of the higher energy barrier for Na+ than K+ at the channel entrance and ion binding sites. In addition, reducing the number of ion binding sites leads to an increase in the permeation rate but a decrease in selectivity. These findings not only hold promise for the design of high-performance membranes but also help understand the mechanism of selective ion transport in biological ion channels.

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