Classification of intraarticular calcaneal fractures: comparison of two classification systems.

PURPOSE: Accurately classifying displaced intraarticular calcaneal fractures (DIACFs) is essential for orthopedic surgeons to choose optimal treatment methods and provide results evaluation and communication. Many authors studying used Sanders classification reported moderate intra- and interobserver reliability. Taking the software opportunity of 3D virtual exarticulation, Goldzak updated French tri-dimensional Utheza classification, providing an alternative framework for classifying DIACFs. The aim of this study was to compare the intra- and interobserver reliability of Sanders versus Goldzak classification systems. METHODS: The CT scans of 30 patients with displaced intraarticular calcaneal fractures, treated in the same trauma center between 2014-2018, were analyzed by 16 medical doctors (specialists and residents in orthopedic surgery, specialists and residents in radiology), and classified according to Sanders and Goldzak classifications. The same images were sent on two separate sessions, in a randomized order. Interobserver reliability and intraobserver reproducibility were assessed using Kappa statistics and Gwet's AC1 coefficient. RESULTS: Interobserver reliability using Gwet reported a value of 0.36 for Goldzak classification and 0.30 for Sanders classification (corresponding to "fair assessment" in both cases). In absence of subclasses, "substantial assessment" was reported for Goldzak classification (Gwet of 0.61) and "moderate assessment" for Sanders classification (Gwet of 0.46). Goldzak system had a greater interobserver reliability in the group of radiology residents. Intraobserver reliability coefficient was 0.60 for Goldzak classification and 0.69 for Sanders classification, indicating a substantial agreement for both classifications. CONCLUSION: Despite the better view of the fracture lines provided by 3D reconstructions, this study failed to prove the superiority of Goldzak classification compared to Sanders classification for DIACFs.

Enhanced Solid-State Fluorescence of Flavin Derivatives by Incorporation in the Metal-Organic Frameworks MIL-53(Al) and MOF-5.

The flavin derivatives 10-methyl-isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were incorporated in two alternative metal-organic frameworks, (MOFs) MIL-53(Al) and MOF-5. We used a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders with one-dimensional (1D) pores and an in-situ approach during the synthesis of MOF-5 with its 3D channel network. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 5.2 wt% for 6F-MIA@MOF-5. For the high incorporation yields the probability to have more than one dye molecule in a pore volume is significant. As compared to the flavins in solution, the fluorescence spectrum of these flavin@MOF composites is broadened at the bathocromic side especially for MIA. Time-resolved spectroscopy showed that multi-exponential fluorescence lifetimes were needed to describe the decays. The fluorescence-weighted lifetime of flavin@MOF of 4 ± 1 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of "solid solutions" for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53 due to the formation of various J-aggregates. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photophysical properties of crystalline MIA and the flavin@MOF composites. In the solid flavins, π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores, single flavin molecules represent a major population and the computed MIA@MOF structures do not find π-stacking interactions with the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. To analyze the orientation of flavins in MOFs, we measured fluorescence anisotropy images of single flavin@MOF-5 crystals and a static ensemble flavin@MIL53 microcrystals, respectively. Based on image information, anisotropy distributions and overall curve of the time-resolved anisotropy curves combined with theoretical calculations, we can prove that all fluorescent flavins species have a defined and rather homogeneous orientation in the MOF framework. In MIL-53, the transition dipole moments of flavins are orientated along the 1D channel axis, whereas in MOF-5 we resolved an average orientation that is tilted with respect to the cubic crystal lattice. Notably, the more hydrophobic 6F-MIA exhibits a higher degree order than MIA. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation, defined orientation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.

Influencing factors of urban innovation and development: a grounded theory analysis.

Urban innovation and development are a core driver for promoting the industrial, economic, and social development of cities. However, the factors that affect the innovation and development of cities lack systematic analysis as well as interaction analysis. Based on a multidimensional perspective, this study suggests that natural, economic, and social factors are three major factors conditioning urban innovation and development. A grounded theoretical qualitative method is further adopted to code relevant research literatures, news reports and interview materials, resulting in an onion factors model. We find that natural factors-including environmental quality, geographic location, and city scale-are prerequisite for conditioning urban innovation and development. Economic factors are also key, including economic level, industrial structure, industrial agglomeration, and technological innovation. Social factors are guarantee factors, including administrative hierarchy, cultural environment, population structure, and government management and services, i.e., they are essential for cities to become adaptable in the current dynamic situation. The study provides theoretical support and practical directions for the formulation of policies for urban innovation development.

Using a socio-ecological framework to understand how 8-12-year-olds build and show digital resilience: A multi-perspective and multimethod qualitative study.

Educationalists', researchers', and policy makers' work on children's digital resilience has marginalised the role of the broader context within which digital resilience is constituted, experienced and derived. We aimed to address this lacuna by exploring how pre-teen's digital resilience operates as a dynamic socio-ecological process. Addressing this aim, we employed participatory methods and thematically analysed eight focus groups with children aged 8-12 years (n = 59) and 20 telephone interviews with parents/carers and teachers of 8-12-year-olds and internet safety experts to examine this issue. We used purposive sampling and collected data over three months (January-March 2020). Our analysis constructed a matrix of main themes, constituent, and cross-cutting sub-themes. By placing this within a socio-ecological framework, we illustrate how pre-teens' digital resilience operates within and across differing four levels (individual, home, community and societal) and four domains (learning, recognising, managing, and recovery). The paper advances the literature by illustrating how children can be supported to build and show digital resilience within and across different levels and domains. It is argued that digital resilience should be re-conceptualised as a collective endeavour involving children at an individual level, parents/carers within home environments, youth workers, civil society, teachers, and schools at a community level, along with governments, policymakers, and the education system and internet corporations at a societal level. We conclude by providing practice and research recommendations guiding those supporting children to facilitate opportunities to thrive online.

Patients' and professionals' perspectives on the consideration of patients' convenient therapy periods as part of personalised rehabilitation: a focus group study with patients and therapists from inpatient neurological rehabilitation.

BACKGROUND: Research on the optimal period for administering health services, especially rehabilitation interventions, is scarce. The aims of this study were to explore the construct of patients' convenient therapy periods and to identify indicators based on the perspectives of patients and different health professionals from inpatient neurological rehabilitation clinics. METHODS: This study was part of a larger project on patients' convenient therapy periods following a mixed methods approach. In the current study a grounded theory approach was employed based on the use of focus group interviews. Focus group interviews were conducted in three different inpatient neurological rehabilitation clinics. Patients and therapists from inpatient neurological rehabilitation clinics who were able to speak and to participate in conversations were included. RESULTS: A total of 41 persons, including 23 patients and 18 therapists, such as music and occupational therapists, participated in a total of six focus group interviews. The analysis of the focus group interviews resulted in the identification of a total of 1261 codes, which could be summarised in fifteen categories. However, these categories could be divided into five indicators and ten impact factors of convenient therapy periods. Identified indicators were verbal and non-verbal communication, mental functions, physiological needs, recreational needs, and therapy initiation. CONCLUSIONS: The results provide initial evidence that convenient therapy periods are clinically relevant for patients and therapists. Different states of patients' ability to effectively participate in a rehabilitation intervention exist. A systematic consideration of patients' convenient therapy periods could contribute to a personalised and more efficient delivery of intervention in neurological rehabilitation. To our knowledge, this study is one of the first attempts to research convenient therapy periods.

Busulfan-cyclophosphamide versus cyclophosphamide-busulfan as conditioning regimen before allogeneic hematopoietic cell transplantation: a prospective randomized trial.

Busulfan and cyclophosphamide (BuCy) is a frequently used myeloablative conditioning regimen for allogeneic hematopoietic cell transplantation (allo-HCT). Theoretical considerations and pharmacological data indicate that application of busulfan prior to subsequent cyclophosphamide (BuCy) may trigger liver toxicity. Reversing the order of application to cyclophosphamide-busulfan (CyBu) might be preferable, a hypothesis supported by animal data and retrospective studies. We performed a prospective randomized trial to determine impact of order of application of Bu and Cy before allo-HCT in 70 patients with hematological malignancy, 33 patients received BuCy and 37 CyBu for conditioning. In the short term, there were minimal differences in liver toxicity favoring CyBu over BuCy, significant only for alanine amino transferase at day 30 (p = 0.03). With longer follow-up at 4 years, non-relapse mortality (6% versus 27%, p = 0.05) was lower and survival (63% versus 43%, p = 0.06) was higher with CyBu compared to BuCy. Other outcomes, such as engraftment (p = 0.21), acute and chronic graft-versus-host disease (p = 0.40; 0.36), and relapse (p = 0.79), were similar in both groups. We prospectively show evidence that the order of application of Cy and Bu in myeloablative conditioning in allo-HCT patients has impact on outcome.

Synthesis and Characterization of Bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) (X = H, p-CH3O, p-Br) with Symmetry- and Distance-Dependent Vibrational Circular Dichroism Enhancement and Sign Inversion.

The enantiopure Schiff bases (R or S)-N-1-(X-C6H4)ethyl-2-hydroxy-1-naphthaldimine {X = H [(R or S)-HL1], p-CH3O [(R or S)-HL2], and p-Br [(R- or S)-HL3]} react with cobalt(II) acetate to give bis[(R or S)-N-1-(X-C6H4)ethyl-2-oxo-1-naphthaldiminato-κ2N,O]-Λ/Δ-cobalt(II) {X = H [Λ/Δ-Co-(R or S)-L1], p-CH3O [Λ/Δ-Co-(R or S)-L2], and p-Br [Λ/Δ-Co-(R or S)-L3]} (1-3), respectively. Induced Λ and Δ chirality originates at the metal center of the C2-symmetric molecule in pseudotetrahedral geometry. Differential scanning calorimetry analyses explored the thermal stability of the complexes, which undergo reversible phase transformation from crystalline solid to isotropic liquid phase for 1 and 3 but irreversible phase transformation for 2. Like other cobalt(II) complexes, compounds 1-3 exhibit a continuous ensemble of absorption and circular dichroism bands, which span from the UV to IR region and can be collected into a superspectrum. Infrared vibrational circular dichroism (IR-VCD) spectra witness the coupling between Co2+-centered low-lying electronic states and ligand-centered vibrations. The coupling produces enhanced and almost monosignate VCD spectra, with both effects being mode-dependent in terms of the A or B symmetry (in the C2 point group) and distance from the Co2+ core.

Insight into the structure-elastic property relationship of calcium silicate glasses: a multi-length scale approach.

Based on a combination of molecular dynamics simulations, and Raman and Brillouin light scattering spectroscopies, we investigate the structure and elastic properties relationship in an archetypical calcium silicate glass system. From molecular dynamics and Raman spectroscopy, we show that the atomic structure at the short and intermediate length scales is made up of long polymerized silicate chains, which adjusts itself by closing the Si-O-Si angles and leaving more space to [CaO]n edge shared polyhedra to strengthen the glass. Using Brillouin spectroscopy, we observe an increase of elastic constants of the glass with the calcium content, as the cohesion of the glass structure is enhanced through an increase of the binding between the cross-linked calcium-silicate frameworks. This result, albeit being simple in its nature, illustrates for the first time the implication of the calcium framework in the elastic behavior of the glass and will contribute substantially to the understanding of the composition-structure-property relationships in multi-component industrial glasses.

Metastable phase equilibria in the ice II stability field. A Raman study of synthetic high-density water inclusions in quartz.

Microthermometric measurements of a synthetic high-density (984 kg m-3) water inclusion in quartz revealed that only part of the super-cooled liquid water (L) transforms to solid ice Ih upon ice nucleation (L → ice Ih + L). While ice nucleation occurs in the ice Ih stability field at -41 °C and 28 MPa the pressure increases instantaneously to 315 MPa into the ice II stability field. At this point, both phases, liquid water and ice Ih are metastable. The coexistence of these two phases was confirmed by Raman spectroscopy and could be traced down to -80 °C. The pressure along this low-temperature metastable extension of the ice Ih melting curve was determined by means of the frequency shift of the ice Ih peak position using both the O-H stretching band around 3100 cm-1 and the lattice translational band around 220 cm-1. At -80 °C and 466 MPa the super-cooled ice Ih melting curve encounters the homogeneous nucleation limit (TH) and the remaining liquid water transformed either to metastable ice IV (ice Ih + L → ice Ih + ice IV) or occasionally to metastable ice III (ice Ih + L → ice Ih + ice III). The nucleation of ice IV resulted in a pressure drop of about 180 MPa. Upon subsequent heating the pressure develops along a slightly negatively sloped ice Ih-ice IV equilibrium line terminating in a triple point at -32.7 °C and 273 MPa, where ice IV melts to liquid water (ice Ih + ice IV → ice Ih + L). Hitherto existing experimental data of the ice IV melting curve (ice IV → L) were found to be in line with the observed ice Ih-ice IV-liquid triple point. If, on the other hand, ice III nucleated at -80 °C (instead of ice IV) the associated pressure drop was about 260 MPa. The ice Ih-ice III-liquid triple point was determined at -22.0 °C and 207 MPa (ice Ih + ice III → ice Ih + L), which is in agreement with previous experimental data.

Effect of a Strategy of Comprehensive Vasodilation vs Usual Care on Mortality and Heart Failure Rehospitalization Among Patients With Acute Heart Failure: The GALACTIC Randomized Clinical Trial.

Importance: Short-term infusions of single vasodilators, usually given in a fixed dose, have not improved outcomes in patients with acute heart failure (AHF). Objective: To evaluate the effect of a strategy that emphasized early intensive and sustained vasodilation using individualized up-titrated doses of established vasodilators in patients with AHF. Design, Setting, and Participants: Randomized, open-label blinded-end-point trial enrolling 788 patients hospitalized for AHF with dyspnea, increased plasma concentrations of natriuretic peptides, systolic blood pressure of at least 100 mm Hg, and plan for treatment in a general ward in 10 tertiary and secondary hospitals in Switzerland, Bulgaria, Germany, Brazil, and Spain. Enrollment began in December 2007 and follow-up was completed in February 2019. Interventions: Patients were randomized 1:1 to a strategy of early intensive and sustained vasodilation throughout the hospitalization (n = 386) or usual care (n = 402). Early intensive and sustained vasodilation was a comprehensive pragmatic approach of maximal and sustained vasodilation combining individualized doses of sublingual and transdermal nitrates, low-dose oral hydralazine for 48 hours, and rapid up-titration of angiotensin-converting enzyme inhibitors, angiotensin receptor blockers, or sacubitril-valsartan. Main Outcomes and Measures: The primary end point was a composite of all-cause mortality or rehospitalization for AHF at 180 days. Results: Among 788 patients randomized, 781 (99.1%; median age, 78 years; 36.9% women) completed the trial and were eligible for primary end point analysis. Follow-up at 180 days was completed for 779 patients (99.7%). The primary end point, a composite of all-cause mortality or rehospitalization for AHF at 180 days, occurred in 117 patients (30.6%) in the intervention group (including 55 deaths [14.4%]) and in 111 patients (27.8%) in the usual care group (including 61 deaths [15.3%]) (absolute difference for the primary end point, 2.8% [95% CI, -3.7% to 9.3%]; adjusted hazard ratio, 1.07 [95% CI, 0.83-1.39]; P = .59). The most common clinically significant adverse events with early intensive and sustained vasodilation vs usual care were hypokalemia (23% vs 25%), worsening renal function (21% vs 20%), headache (26% vs 10%), dizziness (15% vs 10%), and hypotension (8% vs 2%). Conclusions and Relevance: Among patients with AHF, a strategy of early intensive and sustained vasodilation, compared with usual care, did not significantly improve a composite outcome of all-cause mortality and AHF rehospitalization at 180 days. Trial Registration: ClinicalTrials.gov Identifier: NCT00512759.

Bandgap Engineering of Graphene Nanoribbons by Control over Structural Distortion.

Among organic electronic materials, graphene nanoribbons (GNRs) offer extraordinary versatility as next-generation semiconducting materials for nanoelectronics and optoelectronics due to their tunable properties, including charge-carrier mobility, optical absorption, and electronic bandgap, which are uniquely defined by their chemical structures. Although planar GNRs have been predominantly considered until now, nonplanarity can be an additional parameter to modulate their properties without changing the aromatic core. Herein, we report theoretical and experimental studies on two GNR structures with "cove"-type edges, having an identical aromatic core but with alkyl side chains at different peripheral positions. The theoretical results indicate that installment of alkyl chains at the innermost positions of the "cove"-type edges can "bend" the peripheral rings of the GNR through steric repulsion between aromatic protons and the introduced alkyl chains. This structural distortion is theoretically predicted to reduce the bandgap by up to 0.27 eV, which is corroborated by experimental comparison of thus synthesized planar and nonplanar GNRs through UV-vis-near-infrared absorption and photoluminescence excitation spectroscopy. Our results extend the possibility of engineering GNR properties, adding subtle structural distortion as a distinct and potentially highly versatile parameter.

Quantitative Studies on the Structure of Molten Binary Potassium Molybdates by in Situ Raman Spectroscopy and Quantum Chemistry ab Initio Calculations.

The quantitative distribution of different species ( Q ijklm and H ijklmno) in binary potassium molybdate melts has been investigated by in situ high temperature Raman spectroscopy in conjunction with quantum chemistry (QC) ab initio calculations. The symmetric stretching vibrational wavenumbers of molybdenum nonbridging oxygen bonds in high wavenumber range and their respectively corresponding Raman scattering cross sections were determined and analyzed. Deconvolution of the stretching bands of molybdenum nonbridging oxygen bonds of molten Raman spectra by using the Voigt function was carried out. The six-coordinated molybdenum oxygen octahedra [MoO6]6- have been proposed to be present in molten molybdates, apart from the well-known existence of the four-coordinated [MoO4]2- tetrahedra. The quantitative analysis of different species in the molten K2MoO4-MoO3 system and their dependence on the content of MoO3, as well as the relationship with the viscosities of the melts, were also discussed. The quantitative results have been integrated with published data on physical and chemical properties of the melts.

Protecting a Diamond Quantum Memory by Charge State Control.

In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing. Prominent examples are the nitrogen-vacancy (NV) center in diamond, phosphorus dopants in silicon (Si:P), rare-earth ions in solids, and VSi-centers in silicon-carbide. The Si:P system has demonstrated that its nuclear spins can yield exceedingly long spin coherence times by eliminating the electron spin of the dopant. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet. Here, we identify and characterize the positively charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 4. Surprisingly, the new charge state allows switching of the optical response of single nodes facilitating full individual addressability.

Novel Proteomic Assay of Breast Implants Reveals Proteins With Significant Binding Differences: Implications for Surface Coating and Biocompatibility.

BACKGROUND: Silicone elastomer, a ubiquitous biomaterial and main constituent of breast implants, has been used for breast augmentation and reconstruction for over 50 years. Breast implants have direct local and purported systemic effects on normal tissue homeostasis dictated by the chemical and physical presence of the implant. OBJECTIVES: Protein adsorption has been demonstrated to be a key driver of local reactions to silicone. We sought to develop an assay and identify the proteins that coat implants during breast implantation. METHODS: Wound fluid was salvaged from women who had undergone breast reduction and incubated in contact with the surface of 13 commercially available implant surfaces. An in situ digestion technique was optimized to elute bound proteins. Samples were analyzed on an Orbitrap elite analyser, proteins identified in Mascot Demon and analyzed in Progenesis. RESULTS: A total of 822 proteins were identified, bound to the surfaces of the implants. Extracellular proteins were the most abundant ontology, followed by intracellular proteins. Fibrinogen, a proinflammatory protein and Albumin, an anti-inflammatory protein had significant (P < 0.0001) binding differences between the surfaces studied. Complement C3, C5, and factor H were also shown to have significantly different binding affinities for the implants included in the study (P < 0.05). CONCLUSIONS: We have developed a novel assay of breast implant protein binding and demonstrated significant binding affinities for relevant proteins derived from breast tissue wound fluid.

The best cited articles of the European Journal of Orthopaedic Surgery and Traumatology (EJOST): a bibliometric analysis.

European Journal of Orthopaedic Surgery and Traumatology (EJOST) was founded in 1991. It was initially named as Orthopédie-Traumatologie, and since then it is dedicated in sharing knowledge and new evidence in the field of orthopaedics. Within 28 volumes and 157 issues, it has published 3218 scientific articles. In the early years of its distribution, published articles were in French, while the last two decades EJOST only hosts English articles between its pages. By the very beginning of its launch, it has been publishing high-quality research articles in all orthopaedic subspecialties and has gradually become one of the leading journals in its specific subject area. The aim of this study was to identify, analyse and categorize the most frequently cited articles, published by EJOST since its launch.

Oversolubility in the microvicinity of solid-solution interfaces.

Water-solid interactions at the macroscopic level (beyond tens of nanometers) are often viewed as the coexistence of two bulk phases with a sharp interface in many areas spanning from biology to (geo)chemistry and various technological fields (membranes, microfluidics, coatings, etc.). Here we present experimental evidence indicating that such a view may be a significant oversimplification. High-resolution infrared and Raman experiments were performed in a 60 × 20 µm(2) quartz cavity, synthetically created and initially filled with demineralized water. The IR mapping (3 × 3 µm(2) beam size) performed using the SOLEIL synchrotron radiation source displays two important features: (i) the presence of a dangling free-OH component, a signature of hydrophobic inner walls; (ii) a shift of the OH-stretching band which essentially makes the 3200 cm(-1) sub-band predominate over the usual main component at around 3400 cm(-1). Raman maps confirmed these signatures (though less marked than IR's) and afforded a refined spatial distribution of this interfacial signal. This spatial resolution, statistically treated, results in a puzzling image of a 1-3 µm thick marked-liquid layer along the entire liquid-solid interface. The common view is then challenged by this strong evidence that a µm-thick layer analogous to an interphase forms at the solid-liquid interface. The thermodynamic counterpart of the vibrational shifts amounts to around +1 kJ mol(-1) at the interface with a rapidly decreasing signature towards the cavity centre, meaning that vicinal water may form a reactive layer, of micrometer thickness, expected to have an elevated melting point, a depressed boiling temperature, and enhanced solvent properties.

Three-dimensional bicomponent supramolecular nanoporous self-assembly on a hybrid all-carbon atomically flat and transparent platform.

Molecular self-assembly is a versatile nanofabrication technique with atomic precision en route to molecule-based electronic components and devices. Here, we demonstrate a three-dimensional, bicomponent supramolecular network architecture on an all-carbon sp(2)-sp(3) transparent platform. The substrate consists of hydrogenated diamond decorated with a monolayer graphene sheet. The pertaining bilayer assembly of a melamine-naphthalenetetracarboxylic diimide supramolecular network exhibiting a nanoporous honeycomb structure is explored via scanning tunneling microscopy initially at the solution-highly oriented pyrolytic graphite interface. On both graphene-terminated copper and an atomically flat graphene/diamond hybrid substrate, an assembly protocol is demonstrated yielding similar supramolecular networks with long-range order. Our results suggest that hybrid platforms, (supramolecular) chemistry and thermodynamic growth protocols can be merged for in situ molecular device fabrication.

Addressing single nitrogen-vacancy centers in diamond with transparent in-plane gate structures.

For many applications of the nitrogen-vacancy (NV) center in diamond, the understanding and active control of its charge state is highly desired. In this work, we demonstrate the reversible manipulation of the charge state of a single NV center from NV(-) across NV(0) to a nonfluorescent, dark state by using an all-diamond in-plane gate nanostructure. Applying a voltage to the in-plane gate structure can influence the energy band bending sufficiently for charge state conversion of NV centers. These diamond in-plane structures can function as transparent top gates, enabling the distant control of the charge state of NV centers tens of micrometers away from the nanostructure.

Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR.

Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with (13)C and (11)B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and (13)C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.