Scalable Customization of Crystallographic Plane Controllable Lithium Metal Anodes for Ultralong-Lasting Lithium Metal Batteries.

A formidable challenge to achieve the practical applications of rechargeable lithium (Li) metal batteries (RLMBs) is to suppress the uncontrollable growth of Li dendrites. One of the most effective solutions is to fabricate Li metal anodes with specific crystal plane, but still lack of a simple and high-efficient approach. Herein, a facile and controllable way for the scalable customization of polished Li metal anodes with highly preferred (110) and (200) crystallographic orientation (donating as polished Li(110) and polished Li(200), respectively) by regulating the times of accumulative roll bonding, is reported. According to the inherent characteristics of polished Li(110)/Li(200), the influence of Li atomic structure on the electrochemical performance of RLMBs is deeply elucidated by combining theoretical calculations with relative experimental proofs. In particular, a polished Li(110) crystal plane is demonstrated to induce Li+ uniform deposition, promoting the formation of flat and dense Li deposits. Impressively, the polished Li(110)||LiFePO4 full cells exhibit unprecedented cycling stability with 10 000 cycles at 10 C almost without capacity degradation, indicating the great potential application prospect of such textured Li metal. More valuably, this work provides an important reference for low-cost, continued, and large-scale production of Li metal anodes with highly preferred crystal orientation through roll-to-roll manufacturability.

Dual-ROS-scavenging and dual-lingering nanozyme-based eye drops alleviate dry eye disease.

Efficiently removing excess reactive oxygen species (ROS) generated by various factors on the ocular surface is a promising strategy for preventing the development of dry eye disease (DED). The currently available eye drops for DED treatment are palliative, short-lived and frequently administered due to the short precorneal residence time. Here, we developed nanozyme-based eye drops for DED by exploiting borate-mediated dynamic covalent complexation between n-FeZIF-8 nanozymes (n-Z(Fe)) and poly(vinyl alcohol) (PVA) to overcome these problems. The resultant formulation (PBnZ), which has dual-ROS scavenging abilities and prolonged corneal retention can effectively reduce oxidative stress, thereby providing an excellent preventive effect to alleviate DED. In vitro and in vivo experiments revealed that PBnZ could eliminate excess ROS through both its multienzyme-like activity and the ROS-scavenging activity of borate bonds. The positively charged nanozyme-based eye drops displayed a longer precorneal residence time due to physical adhesion and the dynamic borate bonds between phenyboronic acid and PVA or o-diol with mucin. The in vivo results showed that eye drops could effectively alleviate DED. These dual-function PBnZ nanozyme-based eye drops can provide insights into the development of novel treatment strategies for DED and other ROS-mediated inflammatory diseases and a rationale for the application of nanomaterials in clinical settings.

Enhanced Nanotwinned Copper Bonding through Epoxy-Induced Copper Surface Modification.

For decades, Moore's Law has neared its limits, posing significant challenges to further scaling it down. A promising avenue for extending Moore's Law lies in three-dimensional integrated circuits (3D ICs), wherein multiple interconnected device layers are vertically bonded using Cu-Cu bonding. The primary bonding mechanism involves Cu solid diffusion bonding. However, the atomic diffusion rate is notably low at temperatures below 300 °C, maintaining a clear and distinct weak bonding interface, which, in turn, gives rise to reliability issues. In this study, a new method of surface modification using epoxy resin to form fine grains on a nanotwinned Cu film was proposed. When bonded at 250 °C, the interfacial grains grew significantly into both sides of the Cu film. When bonded at 300 °C, the interfacial grains extended extensively, eventually eliminating the original bonding interface.

Corrigendum: Romantic love evolved by co-opting mother-infant bonding.

[This corrects the article DOI: 10.3389/fpsyg.2023.1176067.].

Efficacy of seventh generation bonding agents as desensitizers in patients with dentin hypersensitivity: a randomized clinical trial.

BACKGROUND: Dentin hypersensitivity (DH) is one of the most challenging and persistent dental complaints characterized by transient, intense pain triggered by various stimuli. It affects a significant portion of the global population, predominantly those aged 20-40. This study aims to evaluate the desensitizing efficacy of seventh-generation dentin bonding agents (Single Bond Universal by 3 M ESPE and Xeno-V + by Dentsply) against a control group using Bifluorid 12 by Voco in mitigating DH within a month of the follow-up period. METHODS: This was a single-center, parallel-group, double-blind, controlled randomized clinical trial conducted at Dow University of Health Sciences, Karachi, Pakistan. A total of 105 patients with DH were allocated into three groups for this study. The patients were divided into three groups (Single Bond Universal by 3 M ESPE and Xeno-V + by Dentsply) and the control group containing fluoride varnish (Bifluorid 12 by Voco). Discomfort Interval Scale scores and Schiff Cold Air Sensitivity Scale scores were recorded at baseline, immediately after the intervention, after 01 weeks, and after 01 month. RESULTS: All the materials demonstrated a statistically significant reduction in discomfort and sensitivity (DIS scores p-value 0.01) immediately after 01 week and over a period of 01 month after treatment compared with the baseline scores before application, with no single material proving superior over the one-month observation period. The study also provided insights into dental hygiene practices, with a significant majority using a toothbrush and sensitivity patterns, with cold stimuli being the most common cause of sensitivity. CONCLUSION: The study demonstrates that Single Bond Universal, Xeno V+, and Bifluorid 12 are equally effective in reducing dentin hypersensitivity, with no distinct superiority observed over a one-month period. The findings highlight the potential of fluoride varnishes as a less technique-sensitive and cost-effective option for treating DH, offering valuable insights for future research and clinical practice. TRIAL REGISTRATION: NCT04225247 ( https://clinicaltrials.gov/study/NCT04225247 ), Date of Registration: 13/01/2020. (Retrospectively registered).

Competitive Intramolecular Hydrogen Bonding: Offering Molecules a Choice.

The conformational preferences of N-((6-methylpyridin-2-yl)carbamothioyl)benzamide were studied in solution, the gas phase and the solid state via a combination of NMR, density functional theory (DFT) and single crystal X-ray techniques. This acyl thiourea derivative can adopt two classes of low energy conformation, each stabilized by a different 6-membered intramolecular hydrogen bond (IHB) pseudoring. Analysis in different solvents revealed that the conformational preference of this molecule is polarity dependent, with increasingly polar environments yielding a higher proportion of the minor conformer containing an NH…N IHB. The calculated barrier to interconversion is consistent with dynamic behaviour at room temperature, despite the propensity of 6-membered IHB pseudorings to be static. This work demonstrates that introducing competitive IHB pathways can render static IHBs more dynamic and that such systems could have potential as chameleons in drug design.

Concerning for the solvent-polarity-dependent conformational equilibrium and ESIPT mechanism in Pz3HC system: A novel insight.

In this report, we propose a new insight into the interaction between the solvent-polarity-dependent conformational equilibrium and excited state intramolecular proton transfer (ESIPT) behavior of Pz3HC system in four different polar solvents (polarity order: ACN > THF > TOL > CYC). Using quantum chemistry method, we first announce a coexistence mechanism between Pz3HC-1 and Pz3HC-3 in the ground state in four solvents based on the Boltzmann distribution. In particular, Pz3HC-1 is the principal configuration in non-polar solvent, but Pz3HC-3 is the principal configuration in polar solvent. In addition, the simulated fluorescence spectra interprets the negative solvatochromism effect of Pz3HC-1 and Pz3HC-3 in four solvents. The evidence from intramolecular hydrogen bonding (IHB) parameters and electronic perspective collectively confirms the light-induced IHB enhancement and intramolecular charge transfer (ICT) properties in Pz3HC-1 and Pz3HC-3, which raises the likelihood of the ESIPT process. Combining the calculation of potential energy curve (PEC) and intrinsic reaction coordinate (IRC), we demonstrate that the ESIPT ease of Pz3HC-1 in different polar solvents obeys the order of CYC > TOL > THF > ACN, while the order of ESIPT ease in Pz3HC-3 is opposite. Notably, the ESIPT process of Pz3HC-3 in CYC solvent is accompanied by the twisted intramolecular charge transfer (TICT) process. In addition, we also reveal that the enol* and keto* fluorescence peaks of Pz3HC-3 in CYC solvent are quenched by ISC and TICT process, respectively. Our work not only provides a satisfactory explanation of the novel dynamics mechanism for Pz3HC system, but also brings light to the design and application of new sensing molecules in the future.

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non-Covalent Organocatalysis: An Update.

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview on the most important developments in the last years with a clear focus on experimental studies and on catalysts which act via such non-transient interactions.

Silica-supported ionic liquid for efficient gaseous arsenic oxide removal through hydrogen bonding.

The emission of highly-toxic gaseous As2O3 (As2O3 (g)) from nonferrous metal smelting poses environmental concerns. In this study, we prepared an adsorbent (SMIL-X) by loading an ionic liquid (IL) ([HOEtMI]NTf2) into MCM-41 through an impregnation-evaporation process and then applied it to adsorb As2O3 (g). SMIL-20% exhibited an As2O3 (g) adsorption capacity of 35.48 mg/g at 400 °C, which was 490% times higher than that of neat MCM-41. Characterization of SMIL-X indicated that the IL was mainly supported on MCM-41 through O-H…O bonds formed between the hydroxyl groups (-OH) and the silanol groups (Si-OH) and the O-H…F bonds formed between the C-F groups and the Si-OH groups. The hydrogen bonds significantly contributed to the adsorption of As2O3 (g), with -NH and -OH groups forming hydrogen bonds with As-O species (i.e., N-H…O and O-H…O). This showed superior performance to traditional adsorbents that rely on van der Waals forces and chemisorption. Moreover, after exposure to high concentrations of SO2, the adsorption capacities remained at 76% of their initial values, demonstrating some sulfur resistance. This study presents an excellent adsorbent for the purification of As2O3 (g) and shows promising application potential for treating flue gas emitted by nonferrous metal smelting processes.

Hydrogen bonding dominated self-assembly mechanism of amphiphilic molecules in Chinese Baijiu.

Molecular mechanisms underlying the aging of Chinese Baijiu remained elusive. This study proposed the self-assembly behavior of amphiphilic molecules dominated by hydrogen bonds in Chinese Baijiu for the first time. The self-assembly degree of amphiphilic clusters gradually intensifies with the prolonged storage time of Baijiu, comprehensively characterized at both micro and macro levels. The results indicated that the blue-shift of the Raman hydrogen bond vibrational peak (about 11 cm-1 and 7 cm-1, respectively), the increase in viscosity (5.71% and 2.22%, respectively), and the rise in dielectric constant (95.63% and 94.99%, respectively) during the 17-year cellaring process of Strong-flavor Baijiu and Jiang-flavor Baijiu were consistent with the evolutionary trends observed in molecular dynamics simulations. The essential driving factors of cluster structure alteration of amphiphilic aroma substances in Chinese Baijiu during cellaring were demonstrated from molecular level. This study provided a research approach to comprehending the aging mechanism of Chinese Baijiu from the micro level.

Chemical bonding in phase-change chalcogenides.

Almost all phase-change memory materials (PCM) contain chalcogen atoms, and their chemical bonds have been denoted both as ``electron-deficient'' [sometimes referred to as ``metavalent''] and ``electron-rich'' [``hypervalent'', multicentre]. The latter involve lone-pair electrons. We have performed calculations that can discriminate unambiguously between these two classes of bond and have shown that PCM have electron-rich, 3c-4e (``hypervalent'') bonds. Plots of charge transferred between ($ET$) and shared with ($ES$) neighbouring atoms cannot on their own distinguish between ``metavalent'' and ``hypervalent'' bonds, both of which involve single-electron bonds. PCM do not exhibit ``metavalent'' bonding and are not electron-deficient; the bonding is electron-rich of the ``hypervalent'' or multicentre type. .

Predictors of procedural errors in class II resin composite restorations using bitewing radiographs.

Objective: To identify the potential factors that induce procedural errors during posterior proximal resin composite restorations placed by dental students. Materials and Methods: This retrospective study evaluated 803 bitewing radiographs of posterior proximal resin composite restorations placed by dental students at Imam Abdulrahman bin Faisal University. Atypical radiographic signs of failure were screened, and different patient-, operator-, and clinical-related factors were recorded. Chi-square test was used to examine the relationship between procedural errors and recorded factors. Stepwise adjusted logistic regression model was performed to identify predictors of procedural errors. Results: The most observed errors were internal gaps at the bonding interface and internal voids. Molars had 0.39 the risk of internal voids (odds ratio [OR] = 0.39; confidence interval [CI] = 0.25-0.60; P = <0.0001), 0.41 the risk of sharp angle (OR = 0.41; CI = 0.24-0.68; P = <0.001), and 0.57 the risk of open contact (OR = 0.57; CI = 0.34-0.97; P = 0.04) compared to premolars. Those who were >40 years of age had 1.79 the risk of overhang compared to younger patients (OR = 1.79; CI = 1.04-3.11; P = <0.04). First molars and premolars had 0.64 the risk of overhang compared to second molars and premolars (OR = 0.64; CI = 0.41-1.00; P = 0.04). Junior students had 1.97 the risk of internal gap compared to their senior counterparts (OR = 1.97; CI = 1.20-3.21; P = 0.008). Mesial restorations had 0.38 the risk of external gap compared to mesio-occluso-distal (MOD) restorations (OR = 0.38; CI = 0.19-0.78; P = 0.003). Restorations with a margin coronal to the cemento-enamel junction (CEJ) had 0.44 the risk of external gap compared to those restorations with a margin apical to the CEJ (OR = 0.44; CI = 0.29-0.66; P = <0.0001). Conclusion: Our findings suggested a higher incidence of procedural errors in restoring premolars and MOD cavity preparations. Therefore, it is crucial to enhance the comprehensiveness of laboratory training and expose students to diverse clinical scenarios and various techniques.

Study of Cellulose Dissolution in ZnO/NaOH/Water Solvent Solution and Its Temperature-Dependent Effect Using Molecular Dynamics Simulation.

Cellulose is a biopolymer with numerous advantages that make it an ecological, economical, and high-performing choice for various applications. To fully exploit the potential of cellulose, it is often necessary to dissolve it, which poses a current challenge. The aqueous zinc oxide/sodium hydroxide (ZnO/NaOH/Water) system is a preferred solvent for its rapid dissolution, non-toxicity, low cost, and environmentally friendly nature. In this context, the behavior of cellulose chains in the aqueous solution of ZnO/NaOH and the impact of temperature on the solubility of this polymer were examined through a molecular dynamics simulation. The analysis of the root means square deviation (RMSD), interaction energy, hydrogen bond curves, and radial distribution function revealed that cellulose is insoluble in the ZnO/NaOH solvent at room temperature (T = 298 K). Decreasing the temperature in the range of 273 K to 268 K led to a geometric deformation of cellulose chains, accompanied by a decrease in the number of interchain hydrogen bonds over the simulation time, thus confirming the solubility of cellulose in this system between T = 273 K and T = 268 K.

Longer light-curing time decreases the effect of ageing on composite resin hardness used in root reinforcement.

This study evaluated the hardness of a composite resin used for root reinforcement, considering the light-curing time, root canal region and ageing due to long-term storage. Twenty incisor roots were reinforced using composite resin, varying the photopolymerisation time (40 or 120 s). Following fibre post cementation, the roots were transversely sectioned into coronal, middle and apical regions. Composite hardness was measured initially and after 18 months of water storage. Data underwent repeated measures analysis of variance and Tukey's post hoc tests. The factors 'light-curing time', 'root region' and 'ageing' affected the hardness. Significant interactions were observed between 'light-curing time × root region' and 'ageing × light-curing time'. Regardless of time, resin hardness in the apical region was lower. After ageing, hardness in the coronal and middle regions decreased when the light-curing time was 40 s, while no significant effect on hardness was noted with a light-curing time of 120 s.

Structure-property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives.

Presented here is the design, synthesis, and study of a variety of novel hydrogen-bonding-capable π-conjugated N-heteroacenes, 1,4-dihydropyrazino[2,3-b]quinoxaline-2,3-diones (DPQDs). The DPQDs were accessed from the corresponding weakly hydrogen-bonding dicyanopyrazinoquinoxaline (DCPQ) suspensions with excess potassium hydroxide, resulting in moderate to good yields. Both families of compounds were analyzed by UV-vis and NMR spectroscopy, where the consequences of hydrogen bonding capability could be assessed through the structure-property studies. Conversion of the DCPQs into hydrogen-bonding capable DPQDs results in modulation of frontier MO energies, higher molar extinction coefficients, enhanced crystallinity, and on-average higher thermal stability (where in some cases the 5% weight loss temperature is increased by up to 100 °C). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices.

Vulnerable Baby Perception of Mothers with Infants in the Neonatal Intensive Care Unit: Relationship with Breastfeeding Self-Efficacy and Bonding.

Aim: This study was performed with the aim of investigating the correlation between vulnerable baby perception with breastfeeding self-efficacy and bonding of mothers with infants in the neonatal intensive care unit. Material and Method: The sample for this descriptive and relational search study comprised mothers of 80 healthy infants admitted to the neonatal intensive care unit (NICU) of Ordu University Education and Research Hospital for at least 3 days and at least 1 week past discharge. Collection of data used the Mother and Infant Descriptive Information Form, Vulnerable Baby Scale (VBS), Breastfeeding Self-Efficacy Scale (BSES), and Mother-Infant Bonding Scale (MIBS). Results: The VBS scores for employed mothers were significantly higher than those who were not employed, whereas the VBS scores for mothers with planned pregnancy were significantly higher than those with unplanned pregnancy (p < 0.05). According to the total number of pregnancies, the BSES scores were identified to be statistically significantly different (p < 0.05). The MIBS scores for mothers without mental change related to admission of the infant to NICU were significantly lower than those who were sad/scared (p = 0.015). There was a statistically insignificant correlation between VBS score and BSES score (p > 0.05). There was a positive and very weak statistically significant correlation between VBS score and MIBS score (p = 0.034). As VBS scores increase, MIBS scores increase (higher MIBS = lower bonding). In addition, the effect of VBS score on MIBS score was identified to be statistically significant (p = 0.042). Conclusion: The results of the study found a significant correlation between vulnerable baby perceptions of mothers and mother-infant bonding. As vulnerable baby perceptions increased, mother-infant bonding was identified to decrease. We speculate the breastfeeding self-efficacy and bonding levels of mothers with infants in the NICU should be assessed along with vulnerability perception levels, and necessary support should be provided to reduce vulnerability perceptions by informing mothers about the neonate's status.

Determining the Factors accounting for Reaction Selectivity A Relative Energy Gradient - Interacting Quantum Atoms and Natural Bonding Orbitals Study.

Identifying the main physicochemical properties accounting for the course of a reaction is of utmost importance to rationalize chemical syntheses. To this aim, the relative energy gradient (REG) method is an appealing approach because it is an unbiased and automatic process to extract the most relevant pieces of energy information. Initially formulated within the interacting quantum atoms (IQA) framework for a single reaction, here we extend the REG method to natural bond orbitals (NBO) analysis and to the case of two competitive processes. This development enables the determination of the driving forces of any chemical selectivity. We illustrate the extended REG method on the case study of ring opening in cyclobutenes, which is an important instance of the so-called torquoselectivity.

Decoding the mechanism governing the structural stability of wheat germ agglutinin and its isolated domains: A combined calorimetric, NMR, and MD simulation study.

Wheat germ agglutinin (WGA) demonstrates potential as an oral delivery agent owing to its selective binding to carbohydrates and its capacity to traverse biological membranes. In this study, we employed differential scanning calorimetry and molecular dynamics simulations to comprehensively characterize the thermal unfolding process of both the complete lectin and its four isolated domains. Furthermore, we present the nuclear magnetic resonance structures of three domains that were previously lacking experimental structures in their isolated forms. Our results provide a collective understanding of the energetic and structural factors governing the intricate unfolding mechanism of the complete agglutinin, shedding light on the specific role played by each domain in this process. The analysis revealed negligible interdomain cooperativity, highlighting instead significant coupling between dimer dissociation and the unfolding of the more labile domains. By comparing the dominant interactions, we rationalized the stability differences among the domains. Understanding the structural stability of WGA opens avenues for enhanced drug delivery strategies, underscoring its potential as a promising carrier throughout the gastrointestinal environment.

Design of Soft/Hard Interface with High Adhesion Energy and Low Interfacial Thermal Resistance via Regulation of Interfacial Hydrogen Bonding Interaction.

Adhesion ability and interfacial thermal transfer capacity at soft/hard interfaces are of critical importance to a wide variety of applications, ranging from electronic packaging and soft electronics to batteries. However, these two properties are difficult to obtain simultaneously due to their conflicting nature at soft/hard interfaces. Herein, we report a polyurethane/silicon interface with both high adhesion energy (13535 J m-2) and low thermal interfacial resistance (0.89 × 10-6 m2 K W-1) by regulating hydrogen interactions at the interface. This is achieved by introducing a soybean-oil-based epoxy cross-linker, which can destroy the hydrogen bonds in polyurethane networks and meanwhile can promote the formation of hydrogen bonds at the polyurethane/silicon interface. This study provides a comprehensive understanding of enhancing adhesion energy and reducing interfacial thermal resistance at soft/hard interfaces, which offers a promising perspective to tailor interfacial properties in various material systems.

Comparison of the accuracy of bracket axial positioning with and without radiographic support and according to practitioner experience: A three-dimensional study.

INTRODUCTION: Accurate bracket positioning remains challenging. To avoid angulation errors, some recommend examining the panoramic radiograph during bonding. However, it can cause distortions. Cone-beam computed tomography (CBCT) provides a more precise panoramic reconstruction but with higher radiation doses. The main objective of this study is to compare the accuracy of axial positioning between direct bonding without radiography, with conventional panoramic radiograph, and with panoramic reconstruction from CBCT. The secondary objectives are to evaluate positioning accuracy of each tooth and to assess the influence of practitioner level of experience. METHODS: Thirty practitioners, divided into two groups based on their experience performed direct bonding on a model thrice: without radiography, then with the conventional panoramic radiograph, then with the panoramic reconstruction from CBCT. Models were scanned, and angulation errors were measured using OrthoAnalyzer. Values were compared using the Friedman's test followed by the Bonferroni correction for multiple comparisons (P-value = 0.05). RESULTS: For the low level of experience group, angulation errors were significantly greater than the accepted limit without radiographic reference, and significantly lower with CBCT reconstruction. For the high level of experience group, angulation errors were significantly lower than the accepted limit for the three bonding methods. For every tooth, using the panoramic reconstruction from CBCT as a reference, was the most accurate method, regardless of the level of experience. More experienced practitioners made fewer errors for the three methods. CONCLUSIONS: Panoramic reconstruction from CBCT is the most accurate method to limit angulation errors during direct bonding. Conventional panoramic radiography remains a reliable tool if used with caution. Bonding without any radiographic reference should be avoided especially for less experienced practitioners.