Direct Fabrication of Sub-10 nm Nanopores in WO3 Nanosheets Using Single Swift Heavy Ions.

Extending the fabrication methodology of solid-state nanopores in a wide range of materials is significant in the fields of single molecule detection, nanofluidic devices, and nanofiltration membranes. Here, we demonstrate a new method to directly fabricate size- and density-controllable sub-10 nm nanopores in WO3 nanosheets using single swift heavy ions (SHIs) without any chemical etching process. By selecting ions of different electronic energy losses (Se), nanopores with sizes from 1.8 to 7.4 nm can be created in WO3 nanosheets. The creation efficiency of nanopores achieves ∼100% for Se > 20 keV/nm, and there exists a critical thickness below which nanopores can be created. Combined with molecular dynamics simulations, we propose that the viscosity and surface tension of the transient molten phase caused by SHIs are the key factors for the formation of nanopores. This method paves a way to fabricate solid-state nanopores in materials with a low viscosity and surface tension.

Comparative Analysis of the Biochemical Composition, Amino Acid, and Fatty Acid Contents of Diploid, Triploid, and Tetraploid Crassostrea gigas.

Tetraploid oysters are artificially produced oysters that do not exist in nature. The successful breeding of 100% triploid oysters resolved the difficulties of traditional drug-induced triploids, such as the presence of drug residues and a low triploid induction rate. However, little is known concerning the biochemical composition and nutrient contents of such tetraploids. Therefore, we investigated compositional differences among diploid, triploid, and tetraploid Crassostrea gigas as well as between males and females of diploids and tetraploids. The findings indicated that glycogen, EPA, ∑PUFA, and omega-3 contents were significantly higher in triploid oysters than in diploids or tetraploids; tetraploid oysters had a significantly higher protein content, C14:0, essential amino acid, and flavor-presenting amino acid contents than diploids or triploids. For both diploid and tetraploids, females had significantly higher levels of glutamate, methionine, and phenylalanine than males but lower levels of glycine and alanine. In addition, female oysters had significantly more EPA, DHA, omega-3, and total fatty acids, a result that may be due to the fact that gonadal development in male oysters requires more energy to sustain growth, consumes greater amounts of nutrients, and accumulates more proteins. With these results, important information is provided on the production of C. gigas, as well as on the basis and backing for the genetic breeding of oysters.

Analysis of Volatile Compounds and Flavor Fingerprint Using Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) on Crassostrea gigas with Different Ploidy and Gender.

In this study, GC-IMS was used to analyze the volatile component and flavor profiles of Crassostrea gigas individuals of different ploidy and gender. Principal component analysis was used to explore overall differences in flavor profiles, and a total of 54 volatile compounds were identified. The total volatile flavor contents in the edible parts of tetraploid oysters were significantly higher than in diploid and triploid oysters. The concentrations of ethyl (E)-2-butenoate and 1-penten-3-ol were significantly higher in triploid oysters than in diploid and tetraploid oysters. In addition, the volatile compounds propanoic acid, ethyl propanoate, 1-butanol, butanal, and 2-ethyl furan were significantly higher in females than in males. The volatile compounds p-methyl anisole, 3-octanone, 3-octanone, and (E)-2-heptenal were present in higher levels in male than in female oysters. Overall, different ploidy and gender of oysters are connected with different sensory characteristics, providing new insights for understanding the flavor characteristics of oysters.

Fingerprint Analysis of Volatile Flavor Compounds in Crassostrea gigas of Different Ploidy and Gender under High-Temperature Incubation.

In this study, diploid, triploid, and tetraploid Crassostrea gigas samples were subjected to gas chromatography and ion mobility (GC-IMS) to identify and analyze volatile compounds and flavor fingerprints under conditions of high-temperature incubation. The GC-IMS technology identified a total of 54 volatile components in C. gigas. The contents of 1-octen-3-ol, butyl pentanoate, p-methyl anisole, and 2-methyl-2-hepten-6-one in male oysters were significantly higher than in females, while the contents of phenylacetaldehyde, benzaldehyde, 2-ethyl-3-methylpyrazine, 2-ethylfuran, and 2,4-hexadienal in female oysters were significantly higher than in males. The contents of non-3-en-2-one-M and 1-pentanol in diploids were significantly higher than in triploids and tetraploids, while the content of 2,4-hexadienal in tetraploids was significantly higher than in diploids and tetraploids. The contents of ethyl acetate, ethyl-2-butenoate, and butanal in tetraploids were significantly higher than those in diploids and triploids. The results of a principal components analysis showed that different samples were relatively independently clustered, allowing the ability to distinguish different oyster samples. The chemical fingerprints of volatile compounds of C. gigas with different ploidy and gender under high-temperature incubation were established, and the volatile substance contours of C. gigas were visualized. The results provide a reference for distinguishing the ploidy and gender of C. gigas under conditions of high-temperature incubation.

High-Performance Osmotic Power Generators Based on the 1D/2D Hybrid Nanochannel System.

Extracting clean energy by converting the salinity gradient between river and sea into energy is an effective way to reduce the global pollution and carbon emissions. Reverse electrodialysis (RED) is of great importance to realize the energy conversion assisting the ion-selective membrane. However, its higher ion resistance and lower conversion efficiency results in the undesirable power conversion performance. Here, we demonstrate a 1D/2D hybrid nanochannel system to achieve high osmotic energy conversion and output power. This heterogeneous structure is composed of two structures, in which the subnanometer nanochannels in graphene oxide membrane (GOM) can serve as a selective layer and reduce the ion diffusion energy barrier, while the nanochannel in the polymer can introduce asymmetry to enhance ionic rectification and conversion efficiency. This heterogeneous membrane exhibits excellent cation selectivity and enhanced ionic current rectification (ICR) performance. The application of the GOM/PET hybrid nanochannel system in osmotic energy harvesting is evaluated, and the output power can reach up to 118.2 pW with the energy conversion efficiency of 40.3%. Theoretical calculation indicates that the 1D/2D hybrid system can effectively take the advantage of excellent cation selectivity of 2D lamellar nanochannels to improve its RED performance significantly.

Ionic Transport and Sieving Properties of Sub-nanoporous Polymer Membranes with Tunable Channel Size.

Bioinspired nanoporous membranes show great potential in ionic separation and water filtration by offering high selectivity with less permeation resistance. However, complex processes always limit their applications. Here, we report a convenient approach to introduce ionic selective channels in a micron-thick polycarbonate membrane through swift heavy ion irradiation accompanied by UV sensitization and pulsed-electrical etching. The characteristic dimension of channels was tuned through regulating energy loss of the incident ion and UV sensitization time of the membrane, resulting in the sub-nanoporous membranes with mean channel diameter ranging from <2.4 to 9.7 Å. These membranes showed the voltage-activated ionic transport properties associated with the dehydration effect, and the corresponding I-V characteristics were related to ionic strength, solution pH, ionic type, and channel diameter. It was found that the transmembrane conduction of multivalent ions was severely suppressed compared to monovalent ions, until the size of the membrane channel was comparable to the hydrated diameter of multivalent ions. Ionic sieving experiments also demonstrated the excellent ionic valence selectivity of the membrane. Even for the membrane with a channel diameter close to 1 nm, the Li+/Mg2+ separation ratio was still as high as 40, and an even higher separation ratio was found for Li+/La3+ (>3000).

Controlled crystallinity and crystallographic orientation of Cu nanowires fabricated in ion-track templates.

The hallmark of materials science is the ability to tailor the structures of a given material to provide a desired response. In this work, the structures involving crystallinity and crystallographic orientation of Cu nanowires electrochemically fabricated in ion-track templates have been investigated as a function of fabrication condition. Both single crystalline and polycrystalline nanowires were obtained by adjusting applied voltages and temperatures of electrochemical deposition. The anti-Hall-Petch effect was experimentally evidenced in the polycrystalline nanowires. The dominant crystallographic orientations of wires along [111], [100], or [110] directions were obtained by selecting electrochemical deposition conditions, i.e., H(2)SO(4) concentration in electrolyte, applied voltage, and electrodeposition temperature.

Selectively Enhanced Ion Transport in Graphene Oxide Membrane/PET Conical Nanopore System.

Graphene oxide (GO) has become a promising 2D material in many areas, such as gas separation, seawater desalination, antibacterial materials, and so on because of its abundant oxygen-containing functional groups and excellent dispersibility in various solvents. The graphene oxide membrane (GOM), a laminar and channel-rich structure assembled by stacked GO nanosheets, served as a kind of precise and ultrafast separation material has attracted widespread attention in membrane separation field. To break the trade-off between ion permeability and ion selectivity of separation membrane based on GOM, GOM/conical nanopore system is obtained by spin-coating ultrathin GOM on PET conical nanopore, which possesses ion rectification property. Comparing to pure PET conical nanopore, the existence of GOM not only enhances the cation conductance but also makes the ion rectification ratio increase from 4.6 to 238.0 in KCl solution. Assisted by COMSOL simulation, it is proved that the GOM can absorb large amount of cations and act as cation source to improve the ion selectivity and rectification effect of GOM/conical nanopore system. Finally, the chemical stability of GOM/conical nanopore is also investigated and the corresponding results reveal that the GOM/conical nanopore system can perform the ion rectification behavior in a wider pH range than pure PET conical nanopore. The presented findings demonstrate the great potential applications of GOM/conical nanopore system in ionic logic circuits and sensor systems.

Large Rectification Effect of Single Graphene Nanopore Supported by PET Membrane.

Graphene is an ideal candidate for the development of solid state nanopores due to its thickness at the atomic scale and its high chemical and mechanical stabilities. A facile method was adopted to prepare single graphene nanopore supported by PET membrane (G/PET nanopore) within the three steps assisted by the swift heavy ion irradiation and asymmetric etching technology. The inversion of the ion rectification effect was confirmed in G/PET nanopore while comparing with bare PET nanopore in KCl electrolyte solution. By modifying the wall charge state of PET conical nanopore with hydrochloric acid from negative to positive, the ion rectification effect of G/PET nanopore was found to be greatly enhanced and the large rectification ratio up to 190 was obtained during this work. Moreover, the high ionic flux and high ion separation efficiency was also observed in the G/PET nanopore system. By comparing the "on" and "off" state conductance of G/PET nanopore while immersed in the solution with pH value lower than the isoelectric point of the etched PET (IEP, pH = 3.8), the voltage dependence of the off conductance was established and it was confirmed that the large rectification effect was strongly dependent on the particularly low off conductance at higher applied voltage.

Surface Modification and Damage of MeV-Energy Heavy Ion Irradiation on Gold Nanowires.

Gold nanowires with diameters ranging from 20 to 90 nm were fabricated by the electrochemical deposition technique in etched ion track polycarbonate templates and were then irradiated by Xe and Kr ions with the energy in MeV range. The surface modification of nanowires was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterizations. Different craters with and without protrusion on the gold nanowires were analyzed, and the two corresponding formation mechanisms, i.e., plastic flow and micro-explosion, were investigated. In addition, the sputtered gold nanoparticles caused by ion irradiation were studied and it was confirmed that the surface damage produced in gold nanowires was increased as the diameter of the nanowires decreased. It was also found that heavy ion irradiation can also create stacking fault tetrahedrons (SFTs) in gold nanowires and three different SFTs were confirmed in irradiated nanowires. A statistical analysis of the size distribution of SFTs in gold nanowires proved that the average size distribution of SFT was positively related to the nuclear stopping power of incident ions, i.e., the higher nuclear stopping power of incident ions could generate SFT with a larger average size in gold nanowires.

Controlled Structure of Electrochemically Deposited Pd Nanowires in Ion-Track Templates.

Understanding and controlling structural properties of the materials are crucial in materials research. In this paper, we report that crystallinity and crystallographic orientation of Pd nanowires can be tailored by varying the fabrication conditions during electrochemical deposition in polycarbonate ion-track templates. By changing the deposition temperature during the fabrication process, the nanowires with both single- and poly-crystallinities were obtained. The wires with preferred crystallographic orientations along [111], [100], and [110] directions were achieved via adjusting the applied voltage and temperature during electrochemical deposition.