Unraveling the energy storage mechanism in graphene-based nonaqueous electrochemical capacitors by gap-enhanced Raman spectroscopy.

Graphene has been extensively utilized as an electrode material for nonaqueous electrochemical capacitors. However, a comprehensive understanding of the charging mechanism and ion arrangement at the graphene/electrolyte interface remain elusive. Herein, a gap-enhanced Raman spectroscopic strategy is designed to characterize the dynamic interfacial process of graphene with an adjustable number of layers, which is based on synergistic enhancement of localized surface plasmons from shell-isolated nanoparticles and a metal substrate. By employing such a strategy combined with complementary characterization techniques, we study the potential-dependent configuration of adsorbed ions and capacitance curves for graphene based on the number of layers. As the number of layers increases, the properties of graphene transform from a metalloid nature to graphite-like behavior. The charging mechanism shifts from co-ion desorption in single-layer graphene to ion exchange domination in few-layer graphene. The increase in area specific capacitance from 64 to 145 µF cm-2 is attributed to the influence on ion packing, thereby impacting the electrochemical performance. Furthermore, the potential-dependent coordination structure of lithium bis(fluorosulfonyl) imide in tetraglyme ([Li(G4)][FSI]) at graphene/electrolyte interface is revealed. This work adds to the understanding of graphene interfaces with distinct properties, offering insights for optimization of electrochemical capacitors.

Resolving nanostructure and chemistry of solid-electrolyte interphase on lithium anodes by depth-sensitive plasmon-enhanced Raman spectroscopy.

The solid-electrolyte interphase (SEI) plays crucial roles for the reversible operation of lithium metal batteries. However, fundamental understanding of the mechanisms of SEI formation and evolution is still limited. Herein, we develop a depth-sensitive plasmon-enhanced Raman spectroscopy (DS-PERS) method to enable in-situ and nondestructive characterization of the nanostructure and chemistry of SEI, based on synergistic enhancements of localized surface plasmons from nanostructured Cu, shell-isolated Au nanoparticles and Li deposits at different depths. We monitor the sequential formation of SEI in both ether-based and carbonate-based dual-salt electrolytes on a Cu current collector and then on freshly deposited Li, with dramatic chemical reconstruction. The molecular-level insights from the DS-PERS study unravel the profound influences of Li in modifying SEI formation and in turn the roles of SEI in regulating the Li-ion desolvation and the subsequent Li deposition at SEI-coupled interfaces. Last, we develop a cycling protocol that promotes a favorable direct SEI formation route, which significantly enhances the performance of anode-free Li metal batteries.

In situ electrochemical Raman spectroscopy and ab initio molecular dynamics study of interfacial water on a single-crystal surface.

The dynamics and chemistry of interfacial water are essential components of electrocatalysis because the decomposition and formation of water molecules could dictate the protonation and deprotonation processes on the catalyst surface. However, it is notoriously difficult to probe interfacial water owing to its location between two condensed phases, as well as the presence of external bias potentials and electrochemically induced reaction intermediates. An atomically flat single-crystal surface could offer an attractive platform to resolve the internal structure of interfacial water if advanced characterization tools are developed. To this end, here we report a protocol based on the combination of in situ Raman spectroscopy and ab initio molecular dynamics (AIMD) simulations to unravel the directional molecular features of interfacial water. We present the procedures to prepare single-crystal electrodes, construct a Raman enhancement mode with shell-isolated nanoparticle, remove impurities, eliminate the perturbation from bulk water and dislodge the hydrogen bubbles during in situ electrochemical Raman experiments. The combination of the spectroscopic measurements with AIMD simulation results provides a roadmap to decipher the potential-dependent molecular orientation of water at the interface. We have prepared a detailed guideline for the application of combined in situ Raman and AIMD techniques; this procedure may take a few minutes to several days to generate results and is applicable to a variety of disciplines ranging from surface science to energy storage to biology.

In situ Raman spectroscopy reveals the structure evolution and lattice oxygen reaction pathway induced by the crystalline-amorphous heterojunction for water oxidation.

One of the most successful approaches for balancing the high stability and activity of water oxidation in alkaline solutions is to use amorphous and crystalline heterostructures. However, due to the lack of direct evidence at the molecular level, the nano/micro processes of amorphous and crystalline heterostructure electrocatalysts, including self-reconstruction and reaction pathways, remain unknown. Herein, the Leidenfrost effect assisted electrospray approach combined with phase separation was used for the first time to create amorphous NiO x /crystalline α-Fe2O3 (a-NiO x /α-Fe2O3) nanowire arrays. The results of in situ Raman spectroscopy demonstrate that with the increase of the potential at the a-NiO x /α-Fe2O3 interface, a significant accumulation of OH can be observed. Combining with XAS spectra and DFT calculations, we believe that more OH adsorption on the Ni centers can facilitate Ni2+ deprotonation to achieve the high-valence oxidation of Ni4+ according to HSAB theory (Fe3+ serves as a strong Lewis acid). This result promotes the electrocatalysts to follow the lattice oxygen activation mechanism. This work, for the first time, offers direct spectroscopic evidence for deepening the fundamental understanding of the Lewis acid effect of Fe3+, and reveals the synergistic effect on water oxidation via the unique amorphous and crystalline heterostructures.

In situ Raman spectroscopy reveals the structure and dissociation of interfacial water.

Understanding the structure and dynamic process of water at the solid-liquid interface is an extremely important topic in surface science, energy science and catalysis1-3. As model catalysts, atomically flat single-crystal electrodes exhibit well-defined surface and electric field properties, and therefore may be used to elucidate the relationship between structure and electrocatalytic activity at the atomic level4,5. Hence, studying interfacial water behaviour on single-crystal surfaces provides a framework for understanding electrocatalysis6,7. However, interfacial water is notoriously difficult to probe owing to interference from bulk water and the complexity of interfacial environments8. Here, we use electrochemical, in situ Raman spectroscopic and computational techniques to investigate the interfacial water on atomically flat Pd single-crystal surfaces. Direct spectral evidence reveals that interfacial water consists of hydrogen-bonded and hydrated Na+ ion water. At hydrogen evolution reaction (HER) potentials, dynamic changes in the structure of interfacial water were observed from a random distribution to an ordered structure due to bias potential and Na+ ion cooperation. Structurally ordered interfacial water facilitated high-efficiency electron transfer across the interface, resulting in higher HER rates. The electrolytes and electrode surface effects on interfacial water were also probed and found to affect water structure. Therefore, through local cation tuning strategies, we anticipate that these results may be generalized to enable ordered interfacial water to improve electrocatalytic reaction rates.

Shaping ability of four single-file systems in the instrumentation of second mesiobuccal canals of three-dimensional printed maxillary first molars.

BACKGROUND: This study evaluated and compared the shaping ability of four advanced single-file nickel-titanium (NiTi) systems during the preparation of curved second mesiobuccal (MB2) canals in maxillary first molar replicas fabricated by three-dimensional (3D) printing via micro-computed tomography (Micro-CT) imaging. METHODS: A total of 60 3D-printed maxillary first molar replicas were constructed from one extracted tooth, with an angle of curvature ranging from 15° to 25°. The MB2 canals from these 60 replicas were divided into 4 groups of 15 replicas according to the canal instrumentation system used, namely, Waveone gold (WOG), Reciproc blue (RCB), XP-endo shaper (XPS) and M3-L. The specimens were scanned before and after preparation using Micro-CT. The pre- and post-instrumentation images of each specimen were superimposed, and the amount of resin removed, the change in surface area, the canal transportation, and centering ability were assessed using the Mimics software. Instrumentation time was also recorded. One-way analysis of variance and least significant difference (LSD) tests were used to statistically compare the groups. The significance level was set at 5%. RESULTS: Instrumentation time with M3-L was significantly longer than the other systems (P<0.05). The amount of resin removed and the change in surface area generated by the 4 systems were different at the apical, middle, and coronal thirds, and the total canal (P<0.05). Overall, WOG and XPS resulted in the less change than RCB and M3-L. There was no significant difference among the groups at the middle third regarding canal transportation and centering ability (P>0.05). However, a significant difference was found at the apical level (P<0.05), where RCB showed the poorest centering ability and the highest canal transportation (P<0.05). In addition, XPS resulted in the least canal transportation (P<0.05) at the coronal level, while there was no significant difference between the four groups in terms of centering ability. CONCLUSIONS: The M3-L instrument required more time to prepare the curved MB2 canals compared with the other systems. Overall, WOG and XPS showed the least resin removal and surface area change. M3-L, XPS, and WOG instruments respected the original canal curvature better than RCB files.

Genotype, biofilm formation ability and specific gene transcripts characteristics of endodontic Enterococcus faecalis under glucose deprivation condition.

OBJECTIVE: To study the relationship between the specific gene and biofilm formation ability of seven wild type Enterococcus faecalis (E. faecalis) under glucose deprivation conditions. DESIGN: Wild type E. faecalis (3RC, 5RC, 25RC, 31RC, 33RC, 37RC, 58RC) extracted from the teeth with persistent apical periodontitis were cultured under glucose deprivation conditions and then resequenced. The biofilm formation ability was compared using primary adherence assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The transcriptional level of biofilm formation-related genes (ace, gelE, efa, esp and fsrB) were detected. RESULTS: Genomic resequencing showed that 3RC and 58RC (Class B) were similar, while 5RC, 25RC, 31RC, 33RC and 37RC (Class A) were similar. Based on primary adherence assay, CLSM and SEM results, biofilm formation ability of Class B strains was lower, while Class A strains were higher when compared with control group (0.25 % glucose). Furthermore, compared with control group (0.25 % glucose), the transcriptional levels of ace, efa and fsrB genes were upregulated in all strains; the transcriptional levels of gelE were downregulated in Class B strains, upregulated in Class A strains; the transcriptional levels of esp of Class B strains were downregulated, while upregulated in 25RC, 31RC and 37RC (Class A), and not observed in 5RC and 33RC. CONCLUSION: The genotypes of wild type E. faecalis of different persistent periapical periodontitis teeth are different. The genotype differences and the transcription levels of related virulence genes (ace, gelE, efa, esp and fsrB) are related to the biological phenotype.

Simulation training for ceramic crown preparation in the dental setting using a virtual educational system.

OBJECTIVES: The aim was to evaluate the effectiveness of a pre-clinical training of ceramic crown preparation using the Virtual Educational System for Dentistry. MATERIAL AND METHODS: Fifty-seven dental students were recruited to prepare a ceramic crown under the guidance of the Real-time Dental Training and Evaluation System (RDTES) in order to collect pre-learning data. They participated in the online virtual learning course independently on the Virtual Learning Network Platform (VLNP). One week later, the students were invited to complete their post-learning crown preparation with the RDTES. A questionnaire survey explored students' perceived benefits or drawbacks of the virtual educational system. Students were allocated into Group A (n = 15), B (n = 24) and C (n = 18) based on their pre-learning performance. Differences of assessment results amongst different groups were evaluated by ANOVA and Kruskal-Wallis tests. The pre- and post-learning assessment results in all groups were compared using paired t tests or Wilcoxon signed rank tests. RESULTS: The error scores for four assessment items (instrument selection, preparation section, preparation reduction, preparation surface and profile) and total score of outcome assessment after the virtual learning were significantly different with those before the virtual learning (P < 0.05). There were significant interactions between time and student group in the mean scores of process and outcome assessments (P < 0.001), except for the assessment item "damage of adjacent teeth." CONCLUSION: The application of a Virtual Educational System for Dentistry with the VLNP and RDTES in pre-clinical operative training helps students improve their clinical skills.

High throughput sequencing-based analysis of microbial diversity in dental unit waterlines supports the importance of providing safe water for clinical use.

This study aims to explore the water quality of dental unit waterlines (DUWLs) and the diversity of microbial communities in DUWLs. Water samples from 33 dental chair units (DCUs) were collected, diluted and then spread on sterilized R2A plate for incubation. Subsequently, the microbial colony-forming units per milliliter (CFU/ml) were recorded by an automatic colony analyzer. Total DNA extracted from the rest of the samples was tested on the Illumina MiSeq PE300 platform. T-test and Kruskal-Wallis rank test were adopted for statistical analysis. Significance was assumed at a P<0.05. After incubation, the average total microbial count was 21,413.13±17,861.00CFU/ml. High-throughput sequencing revealed 10 bacterial phyla, including 9 identified and 1 unclassified phyla. Totally 63 sequences were identified at the genus level, including 42 genera, 3 tentative species and 18 unclassified genera. In addition, 7 potential human pathogenic bacteria were detected. In summary, department, brand and service life of DCUs do not influence the water quality of DUWLs significantly. The diversity of microbial communities in DUWLs is abundant and includes both pathogenic and some unknown bacteria.