Reductive Doping Inhibits the Formation of Isomerization-Derived Structural Defects in N-doped Poly(benzodifurandione) (n-PBDF).

Recently, solution-processable n-doped poly(benzodifurandione) (n-PBDF) has been made through in-situ oxidative polymerization and reductive doping, which exhibited exceptionally high electrical conductivities and optical transparency. The discovery of n-PBDF is considered a breakthrough in the field of organic semiconductors. In the initial report, the possibility of structural defect formation in n-PBDF was proposed, based on the observation of structural isomerization from (E)-2H,2'H-[3,3'-bibenzofuranylidene]-2,2'-dione (isoxindigo) to chromeno[4,3-c]chromene-5,11-dione (dibenzonaphthyrone) in the dimer model reactions. In this study, we present clear evidence that structural isomerization is inhibited during polymerization. We reveal that the dimer (BFD1) and the trimer (BFD2) can be reductively doped by several mechanisms, including hydride transfer, forming charge transfer complexes (CTC) or undergoing an integer charge transfer (ICT) with reactants available during polymerization. Once the hydride transfer adducts, the CTC, or the ICT product forms, structural isomerization can be effectively prevented even at elevated temperatures. Our findings provide a mechanistic understanding of why isomerization-derived structural defects are absent in n-PBDF backbone. It lays a solid foundation for the future development of n-PBDF as a benchmark polymer for organic electronics and beyond.

Preparation of high performance porous carbon by microwave synergistic nitrogen/phosphorus doping for efficient removal of Cu2+ via capacitive deionization.

Sargassum biochar has potential advantages as an electrode material due to its natural microscopic pore channels. However, conventional pyrolysis method is prone to thermal damage to the biochar, and incapable to form a complete pore structure resulting in poor biochar electrode performance. In this study, a strategy of microwave pyrolysis coupled with KOH activation was used to prepare nitrogen/phosphorus double-doped graded porous biochar (STC) using ammonium dihydrogen phosphate as dopant. The carbon material STC-1.24-800 prepared by the optimal parameters had a high specific surface area (SSA) of 1367.6 m2 g -1 and a total pore volume of 1.499 cm3 g-1. The precise inside-out heating characteristics of microwave facilitated the generation of suitable meso-micropore distribution ratios in carbon, and the graded porous structure provided abundant active sites for charge accumulation and ion diffusion. The doped nitrogen/phosphorus atoms responding to the microwave field, generated spin to promote microwave absorption, introducing surface structural defects to produce electron density differences. The change in the nature of the electron donor and its electron density enhanced the electrical conductivity and chemical stability of STC. Nitrogen/phosphorus polar surface functional groups improved hydrophilicity and wettability. STC-1.24-800 had a higher specific capacitance of 531 F g-1 and exhibits great cycle performance in capacitive deionization (CDI) applications (1.0 V, 50 mg L-1 Cu2+) as well as adsorption performance (56.16 mg g -1). The present work can provide a novel feasible idea for preparing diatomically doped graded porous biochar for CDI electrode application by microwave irradiation.

Experimental Study of Deep Submersible Structure Defect Monitoring Based on Flexible Interdigital Transducer Surface Acoustic Wave Technology.

In view of the shortage of structural defect monitoring methods for deep submersibles, numerical simulation and experimental research on underwater SAW propagation based on interdigital transducers are carried out in this paper. PVDF interdigital transducer (PVDF-IDT) has shown considerable potential in the application of structural health monitoring because of its micro size, soft material characteristics, and the characteristics of long-term bonding on the surface of the tested structure. In order to realize the application of IDT on submersible or underwater structures, it is necessary to understand the influence of underwater environment on IDTs with different structures. The underwater attenuation of IDT with 2-5 mm wavelength and the underwater attenuation of Lamb (A0 mode) wave on a 4 mm thick titanium alloy plate is obtained through COMSOL software simulation. The experimental verification shows that the simulation results match with the actual situation, which proves that COMSOL software can accurately calculate the acoustic attenuation of surface waves at the solid-liquid interface. At the same time, the underwater attenuation of IDT with different structures is very different, providing important design parameters for the underwater interdigital transducer. In this paper, it is found that the Lamb wave has significant advantages over the Rayleigh wave in the health monitoring of underwater thin plate structures.

Eco-friendly cubic-ZnS coupled Cu7S4 spines on chitosan matrix: Unravelling defect-engineered nanoplatform for the photodegradation of p-chlorophenol.

Novel ZnS-Cu7S4 nanohybrid supported on chitosan matrix, as an ideal photocatalyst, was fabricated by the sonochemical method wherein high-resolution transmission electron microscopy (HRTEM) and X-ray powder diffraction (XRD) analysis confirmed the co-existence of both ZnS and Cu7S4; presence of vacancy sites in ZnS was verified by electron paramagnetic resonance (EPR) analysis and their introduction could promote two-photon excitation facilitated visible light response and charge transport/separation. The type II interface is formed in the ZnS-Cu7S4/Chitosan heterojunction owing to interstitial states that promote charge separation. The ZnS-Cu7S4/Chitosan was used for the photodegradation of a pharmaceutical pollutant, p-chlorophenol (PCP); over 98.8% of PCP photodegradation was achieved under visible-light irradiation where the ensued ·O2- and ·OH serve a key role in the photodegradation of PCP. In vitro cytotoxicity studies substantiated that the ZnS-Cu7S4/Chitosan is nontoxic to the ecosystem and human beings and endowed with promising photodegradation properties and accessibility via an environmentally friendly design, bodes well for its potential remediation applications.

Time-dependent Phosphorescence Color of Carbon Dots in Binary Salt Matrices through Activations by Structural Confinement and Defects for Dynamic Information Encryption.

The emergence of time-dependent phosphorescence color (TDPC) materials has taken information encryption to high-security levels. However, due to the only path of exciton transfer, it is almost impossible to obtain TDPC for chromophores with a single emission center. Theoretically, in inorganic-organic composites, the exciton transfer of organic chromophores depends on the inorganic structure. Here, we assign two structural effects to inorganic NaCl by metal (Mg2+ or Ca2+ or Ba2+ ) doping, which triggers the TDPC performance of carbon dots (CDs) with a single emission center. The resulting material is used for multi-level dynamic phosphorescence color 3D coding to achieve information encryption. The structural confinement activates the green phosphorescence of CDs; while the structural defect activates tunneling-related yellow phosphorescence. Such simply doped inorganic matrices can be synthesized using the periodic table of metal cations, endowing chromophores with tremendous control over TDPC properties. This demonstration extends the design view of dynamic luminescent materials.

Long-term outcome in apparently healthy children with increased nuchal translucency in the first trimester screening.

INTRODUCTION: Increased nuchal translucency is known to be associated with chromosomal and structural defects and genetic syndromes. Little is known about the overall long-term outcome of euploid children after increased nuchal translucency. The aims of this study were to assess the additional structural defects diagnosed after discharge from the delivery hospital and the long-term overall outcome of euploid children after increased nuchal translucency and normal second trimester anomaly scan. MATERIAL AND METHODS: All children from singleton euploid pregnancies during 2002-2007 with increased nuchal translucency in the first trimester screening, normal second trimester anomaly scan, and discharged as apparently healthy were included. Data on the structural defects and genetic disorders diagnosed until 2012 were retrieved from hospital databases and national registers. Previously published data of structural defects diagnosed after birth but before discharge and of severe neurodevelopmental impairment and genetic syndromes was added. RESULTS: The cohort included 733 children. During the follow-up time (mean 6.5 years), major structural defects were observed in 10 (1.4%), genetic disorders in two (0.3%), and minor defects in 23 (3.1%) children. In addition, there were 42 previously published major structural defects and major neurodevelopmental impairment or genetic disorders. Adding these results together, major health problems were detected in 54 (7%) euploid children with increased fetal nuchal translucency and normal findings in second trimester anomaly scan. CONCLUSION: Although only few additional major structural defects are diagnosed during the follow-up after increased fetal nuchal translucency, 7% of fetuses assumed to be healthy after second trimester anomaly scan have a major health impairment.

Structural Defect-Enabled Magnetic Neutrality Nanoprobes for Ultra-High-Field Magnetic Resonance Imaging of Isolated Tumor Cells in Vivo.

The identification of metastasis "seeds," isolated tumor cells (ITCs), is of paramount importance for the prognosis and tailored treatment of metastatic diseases. The conventional approach to clinical ITCs diagnosis through invasive biopsies is encumbered by the inherent risks of overdiagnosis and overtreatment. This underscores the pressing need for noninvasive ITCs detection methods that provide histopathological-level insights. Recent advancements in ultra-high-field (UHF) magnetic resonance imaging (MRI) have ignited hope for the revelation of minute lesions, including the elusive ITCs. Nevertheless, currently available MRI contrast agents are susceptible to magnetization-induced strong T2-decaying effects under UHF conditions, which compromises T1 MRI capability and further impedes the precise imaging of small lesions. Herein, this study reports a structural defect-enabled magnetic neutrality nanoprobe (MNN) distinguished by its paramagnetic properties featuring an exceptionally low magnetic susceptibility through atomic modulation, rendering it almost nonmagnetic. This unique characteristic effectively mitigates T2-decaying effect while concurrently enhancing UHF T1 contrast. Under 9 T MRI, the MNN demonstrates an unprecedentedly low r2/r1 value (≈1.06), enabling noninvasive visualization of ITCs with an exceptional detection threshold of ≈0.16 mm. These high-performance MNNs unveil the domain of hitherto undetectable minute lesions, representing a significant advancement in UHF-MRI for diagnostic purposes and fostering comprehensive metastasis research.

Investigation on Nanocomposites of Polysulfone and Different Ratios of Graphene Oxide with Structural Defects Repaired by Cellulose Nanocrystals.

In this manuscript, nanofillers of graphene oxide (GO) and cellulose nanocrystal (CNC) with different weight ratios (G/C ratios), named GC 2:1, GC 4:1, GC 8:1, GC 16:1, and GC 32:1, were successfully prepared. Characterization methods such as Raman spectroscopy, X-ray photoelectron spectrometry (XPS), and thermogravimetric analysis (TGA) were performed. Additionally, the effects of these samples on the thermal stability, mechanical properties, and gas barrier properties of polysulfone (PSF) nanocomposites were investigated. A hydrophilic interaction took place between CNC and GO; as a consequence, CNCs were modified on the surface of GO, thus repairing the structural defects of GO. With the increase in G/C ratios, the repair effect of insufficient CNCs on the defects of GO decreased. The G/C ratio had a great influence on the improvement of mechanical properties, thermal stability, and gas barrier properties of nanocomposites. Compared with PSF/GC 2:1 and PSF/GC 32:1, the differences in the growth rates of tensile strength, elongation at break, and Young's modulus were 30.0%, 39.4%, and 15.9%, respectively; the difference in Td 3% was 7 °C; the difference in decline rate of O2 permeability was 40.0%.

Association between Dentofacial Features and Bullying from Childhood to Adulthood: A Systematic Review.

Bullying occurs when an individual is repeatedly victimised by negative actions performed by peers. As oral features, like malocclusion and dental structural defects, can promote psychological distress, which is also found in those who are bullied, we aimed to study the association between orofacial conditions and bullying. A systematic review (PROSPERO CRD42022331693), including articles dealing with bullying and dentofacial traits, was performed following the PRISMA chart. The iterative search of eligible publications was carried out on 27 March 2023 on four databases (PubMed, PubPsych, Web of Science and Cochrane Reviews) and in the grey literature. Among the 25 articles included, 4 referred to qualitative studies, which analysed 632 interviews with children, 8 interviews with parents, 292 letters, and 321 Twitter posts. The other 21 were cross-sectional studies, which included 10,026 patients from 7 to 61 years old. Two of the qualitative studies and seven of the cross-sectional studies rated a low risk of bias, according to Joanna Briggs Institute's Critical Appraisal Tools. The majority of studies (88%) reported a relationship between malocclusion or structural defects and exposure to bullying among young adolescents. Structural dental abnormalities and severe malocclusion should be managed, among others, for psychological questions because they crystallise the loss of self-confidence and increase the risk of bullying.

Engineering the Structural Defects of Spinel Oxide Nanoneedles by Doping of V for a Highly Efficient Oxygen Evolution Reaction.

Rational design of multi-structural defects in the transition-metal oxides is a very alluring and challenging strategy to significantly improve its oxygen evolution reaction (OER) performance. Herein, a simple and promising element doping approach is demonstrated to fabricate a poor-crystalline V-doping CuCo2O4 (V-CuCo2O4) nanoneedle with rich oxygen vacancies (Vo), partially amorphous phase, and Co2+ defects on the carbon fiber (CF) (V-CuCo2O4/CF). The results indicate that the V doping could further weaken the crystallinity of V-CuCo2O4, providing the thoroughfares for the convenience of electrolyte penetration and the exposure of active sites. Meanwhile, [CoO6] octahedron in the V-CuCo2O4 lattice is gravely distorted due to a strong electronic interaction between the doped V and Co atoms, creating more Co2+ active species. With the merits of these multiple structural defects, V-CuCo2O4/CF exhibits rich active sites, and its intrinsically electrocatalytic activity is significantly enhanced. The optimized V-CuCo2O4/CF electrocatalyst has a significantly enhanced OER activity with a required low overpotential of ∼204 and ∼246 mV at a current density of 100 and 300 mA cm-2, respectively, a small Tafel slope of 40.7 mV dec-1, and excellent stability in an alkaline medium. Furthermore, the results from the projected partial density of states calculation not only demonstrate that the 3-fol-coordinated Co near Vo bonded with Cu and V sites (Cu-Co(surf-Vo)-V) exhibits an enhanced electronic transfer activity but also reveal that the doped V could protect the Co sites from the deactivation by intermediates overbinding on the V sites. This work provides new insights into structure engineering of spinel phase copper cobaltite, resulting in significantly boosting electrocatalytic OER activity.

Resistive Switching in Few-Layer Hexagonal Boron Nitride Mediated by Defects and Interfacial Charge Transfer.

We present resistive switching (RS) behavior of few-layer hexagonal boron nitride (h-BN) mediated by defects and interfacial charge transfer. Few-layer h-BN is grown by metal-organic chemical vapor deposition and used as active RS medium in Ti/h-BN/Au structure, exhibiting clear bipolar RS behavior and fast switching characteristics about ∼25 ns without an initial electroforming process. Systematic investigation on microstructural and chemical characteristics of the h-BN reveals that there are structural defects such as homoelemental B-B bonds at grain boundaries and nitrogen vacancies, which can provide preferential pathways for the penetration of Tix+ ions through the h-BN film. In addition, the interfacial charge transfer from Ti to the h-BN is observed by in situ X-ray photoelectron spectroscopy. We suggest that the attractive Coulomb interaction between positively charged Tix+ ions and the negatively charged h-BN surface as a result of the interfacial charge transfer facilitates the migration of Tix+ ions at the Ti/h-BN interface, leading to the facile formation of conductive filaments. We believe that these findings can improve our understanding of the fundamental mechanisms involved in RS behavior of h-BN and contribute a significant step for the future development of h-BN-based nonvolatile memory applications.

Structural defects in 2D MoS2 nanosheets and their roles in the adsorption of airborne elemental mercury.

In this research, ab initio calculations and experimental approach were adopted to reveal the mechanism of Hg0 adsorption on MoS2 nanosheets that contain various types of defects. The ab initio calculation showed that, among different structural defects, S vacancies (Vs) in the MoS2 nanosheets exhibited outstanding potential to strongly adsorb Hg0. The MoS2 material was then prepared in a controlled manner under conditions, such as temperature, concentration of precursors, etc., that were determined by adopting the new method developed in this study. Characterisation confirmed that the MoS2 material is of graphene-like layered structure with abundant structural defects. The integrated dynamic and steady state (IDSS) testing demonstrated that the Vs-rich nanosheets showed excellent Hg0 adsorption capability. In addition, ab initial calculation on charge density difference, PDOS, and adsorption pathways revealed that the adsorption of Hg0 on the Vs-rich MoS2 surface is non-activated chemisorption.

Disorder Enhanced Superconductivity toward TaS2 Monolayer.

Appearance of disorder is commonly known as detrimental to two-dimensional (2D) superconductivity, and typically results in decrement of the critical transition temperature ( Tc). Herein, an anomalous enhancement of superconductivity was observed in TaS2 monolayer with function of disorder induced by structural defect. Owing to controlled pore density by acid concentration during chemical exfoliation, the disorder level in TaS2 framework can be effectively regulated. Dome-shaped behavior was uncovered in disorder dependence of superconductivity toward the chemically functionalized TaS2 monolayers, with Tc enhanced from 2.89 to 3.61 K when below critical disorder level. The disorder-engineered Tc enhancement, which distinctly differs from monotonic decrement in deposited 2D superconductors, can be ascribed to the increment of carrier density induced by Ta atom absence. The exotic superconducting enhancement would give help to deeply understand the correlation between superconductivity and disorder in 2D system.

Insight into morphology and structure of different particle sized kaolinites with same origin.

The particle size, morphology, crystallinity order and structural defects of four kaolinite samples are characterized by the techniques including particle size analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The particle size of four kaolinite samples gradually increases. Four samples all belong to the ordered kaolinite and show a decrease in structural order with the increase of kaolinite particle size. The changes of structural defect are proved by the increase of the band splitting in Raman spectroscopy, the decrease of the intensity of absorption bands in infrared spectroscopy, and the decrease of equivalent silicon atom and the increase of non-equivalent aluminum atom in MAS NMR spectroscopy. The differences in morphology and structural defect are attributed to the broken bonds of Al-O-Si, Al-O-Al and Si-O-Si and the Al substitution for Si in tetrahedral sheets.