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Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

Densifying hydrogen in a metal-organic framework (MOF) at moderate pressures can circumvent challenges associated with high-pressure compression. The highly tunable structural and chemical composition in MOFs affords vast possibilities to optimize binding interactions. At the heart of this search are the nanoscale characteristics of molecular adsorption at the binding site(s). Using density functional theory (DFT) to model binding interactions of hydrogen to the exposed metal site of cation-exchanged MFU-4l, we predict multiple hydrogen ligation of H2 at the first coordination sphere of V(II) in V(II)-exchanged MFU-4l. We find that the strength of this binding between the metal site and H2 molecules can be tuned by altering the halide counterion adjacent to the metal site and that the fluoride containing node affords the most favorable interactions for high-density H2 storage. Using energy decomposition analysis, we delineate electronic contributions that enable multiple hydrogen ligation and demonstrate its benefits for hydrogen adsorption and release at modest pressures.

Oxygen is a critical gas in numerous industries and is produced globally on a gigatonne scale, primarily through energy-intensive cryogenic distillation of air. The realization of large-scale adsorption-based air separations could enable a significant reduction in associated worldwide energy consumption and would constitute an important component of broader efforts to combat climate change. Certain small-scale air separations are carried out using N2-selective adsorbents, although the low capacities, poor selectivities, and high regeneration energies associated with these materials limit the extent of their usage. In contrast, the realization of O2-selective adsorbents may facilitate more widespread adoption of adsorptive air separations, which could enable the decentralization of O2 production and utilization and advance new uses for O2. Here, we present a detailed evaluation of the potential of metal-organic frameworks (MOFs) to serve as O2-selective adsorbents for air separations. Drawing insights from biological and molecular systems that selectively bind O2, we survey the field of O2-selective MOFs, highlighting progress and identifying promising areas for future exploration. As a guide for further research, the importance of moving beyond the traditional evaluation of O2 adsorption enthalpy, ΔH, is emphasized, and the free energy of O2 adsorption, ΔG, is discussed as the key metric for understanding and predicting MOF performance under practical conditions. Based on a proof-of-concept assessment of O2 binding carried out for eight different MOFs using experimentally derived capacities and thermodynamic parameters, we identify two existing materials and one proposed framework with nearly optimal ΔG values for operation under user-defined conditions. While enhancements are still needed in other material properties, the insights from the assessments herein serve as a guide for future materials design and evaluation. Computational approaches based on density functional theory with periodic boundary conditions are also discussed as complementary to experimental efforts, and new predictions enable identification of additional promising MOF systems for investigation.

The widespread implementation of H2 as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of -15 to -25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal-organic framework (MOF) V2Cl2.8(btdd) (H2btdd, bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak π acids. Significantly, gas adsorption data reveal that this material binds H2 with an enthalpy of -21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)-dihydrogen complexation is characterized by a combination of techniques. From powder neutron diffraction data, a V-D2(centroid) distance of 1.966(8) Å is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the H-H stretch was identified, and it displays a red shift of 242 cm-1. Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium dπ and H2 σ* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly π-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations1-4. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N2, through backbonding interactions5-7, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates8. Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N2 capacities and selectivities for the removal of N2 from mixtures with CH4, while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents.

A new plasma dental probe (PDP), powered with 4-6.kV ~100-ns electric pulses at repetition rates of up to 2 kHz, generates a room-temperature > 2-cm-long ~2-mm-diameter plasma plume at ambient atmospheric pressure. The shape of the plasma plume depends on the gas flow rate and the pulse voltage. Growth of Bacillus atrophaeus on nutrient agar plates is completely inhibited by exposure to both He and He/(l%)[O.sub.2] plasmas for 60 s. A 300-s treatment with the He/(l%)[O.sub.2] plasma disinfected a human tooth root canal colonized with saliva-derived biofilms, demonstrating the potential of the PDP as a simple, safe, and effective tool or adjunct for the disinfection of root canals during endodontic therapy. He/(l%)[O.sub.2] plasma is more effective than He alone for B. atrophaeus growth inhibition, and the emission spectrum of the He--[O.sub.2] plasma supports the identification of atomic oxygen as the likely primary reactive chemical species contributing to bacterial inactivation. Index Terms--Atmospheric pressure, bacteria, disinfection, plasma torch, sterilization.

The aim was to assess the effect of XP‐endo Finisher (XPF) on multispecies biofilm removal, in comparison with passive ultrasonic irrigation (PUI) and conventional syringe irrigation (CSI), by scanning electron microscope (SEM). Fifty mandibular first premolars were instrumented, longitudinally sectioned. The split halves were incubated for 4 days with a broth obtained from three bacteria strains: Enterococcus faecalis, Eikenella corrodens and Streptococcus anginosus. Subsequently, the re‐approximated split halves were irrigated with 4% sodium hypochlorite (NaOCl) or water using CSI, and the final irrigation protocols were CSI with 4% NaOCl (CSI+4%NaOCl), PUI+4%NaOCl, XPF+4%NaOCl and CSI+water. The analysis of biofilm removal was performed using SEM images. There were no differences between PUI and XPF (P > 0.05), and both groups promoted higher biofilm removal than CSI+4%NaOCl and CSI+water groups (P < 0.05). It can be concluded the multispecies biofilm removal was significantly improved using XPF and PUI when compared to CSI. [ABSTRACT FROM AUTHOR]

Cutting efficiency of Reciproc R25 (REC) and Reciproc blue R25 (REB) at different inclinations was evaluated. Sixty new files were tested at 90°, 70° and 45° of inclination in relation to the sample (n = 10), using a customised machine. All files were activated in reciprocation against standardised gypsum blocks for 120 s. Cutting efficiency was determined by measuring the block weight loss with an analytical balance and measuring the length of the block surface cut using a digital calliper. Data were statistically analysed (two‐way ANOVA, Bonferroni t‐test) with the significance level set at P < 0.05. There was no difference for REC among the tested angles. REB had no statistical difference between 90° and 70°; however, its cutting efficiency significantly increased at 45°. There was a significant difference between REC and REB at 45° only. Under these conditions, increased file inclination to 45° and blue heat treatment improved cutting efficiency of reciprocating files. [ABSTRACT FROM AUTHOR]

The hypothesis that a cold plasma jet has the antimicrobial effect against Enterococcus faecalis biofilms was tested in vitro. 27 hydroxyapatite discs were incubated with E. faecalis for six days to form a monoculture biofilm on the disc surface. The prepared substrata were divided into three groups: the negative control, the positive control (5.25% NaOCl solution), and the plasma treatment group. Resultant colony-forming unit counts were associated with observations of bacterial cell morphology changes using scanning electron microscopy (SEM). Treatment of E. faecalis biofilm with the plasma and 5.25% NaOCl for 5min resulted in 93.1% and 90.0% kill (P < 0.0001), respectively. SEM detected that nearly no intact bacteria were discernible for the plasmaexposed HA disc surfaces. The demonstrated bactericidal effect of the plasma with direct surface contact may be due to the enhanced oxidation by the locally produced reactive plasma species. [ABSTRACT FROM AUTHOR]

A new plasma dental probe (PDP), powered with 4-6-kV ∼100-ns electric pulses at repetition rates of up to 2 kHz, generates a room-temperature > 2-cm-long ∼2-mm-diameter plasma plume at ambient atmospheric pressure. The shape of the plasma plume depends on the gas flow rate and the pulse voltage. Growth of Bacillus atrophaeus on nutrient agar plates is completely inhibited by exposure to both He and He/(1%)O2 plasmas for 60 s. A 300-s treatment with the He/(1%)O2 plasma disinfected a human tooth root canal colonized with saliva-derived bioflims, demonstrating the potential of the PDP as a simple, safe, and effective tool or adjunct for the disinfection of root canals during endodontic therapy. He/(1%)O2 plasma is more effective than He alone for B. atrophaeus growth inhibition, and the emission spectrum of the He-O2 plasma supports the identification of atomic oxygen as the likely primary reactive chemical species contributing to bacterial inactivation. [ABSTRACT FROM AUTHOR]

Oxygen is a critical gas in numerous industries and is produced globally on a gigatonne scale, primarily through energy-intensive cryogenic distillation of air. The realization of large-scale adsorption-based air separations could enable a significant reduction in associated worldwide energy consumption and would constitute an important component of broader efforts to combat climate change. Certain small-scale air separations are carried out using N 2 -selective adsorbents, although the low capacities, poor selectivities, and high regeneration energies associated with these materials limit the extent of their usage. In contrast, the realization of O 2 -selective adsorbents may facilitate more widespread adoption of adsorptive air separations, which could enable the decentralization of O 2 production and utilization and advance new uses for O 2 . Here, we present a detailed evaluation of the potential of metal-organic frameworks (MOFs) to serve as O 2 -selective adsorbents for air separations. Drawing insights from biological and molecular systems that selectively bind O 2 , we survey the field of O 2 -selective MOFs, highlighting progress and identifying promising areas for future exploration. As a guide for further research, the importance of moving beyond the traditional evaluation of O 2 adsorption enthalpy, Δ H , is emphasized, and the free energy of O 2 adsorption, Δ G , is discussed as the key metric for understanding and predicting MOF performance under practical conditions. Based on a proof-of-concept assessment of O 2 binding carried out for eight different MOFs using experimentally derived capacities and thermodynamic parameters, we identify two existing materials and one proposed framework with nearly optimal Δ G values for operation under user-defined conditions. While enhancements are still needed in other material properties, the insights from the assessments herein serve as a guide for future materials design and evaluation. Computational approaches based on density functional theory with periodic boundary conditions are also discussed as complementary to experimental efforts, and new predictions enable identification of additional promising MOF systems for investigation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: The purpose of the study was to evaluate the effectiveness of different root canal disinfection techniques in the elimination of a multi-species biofilm from inside the root canal., Material and Methods: Fifty mandibular first premolars were used in the present study, standardized to 11mm of root length, and instrumented with a reciprocation system Reciproc, (VDW GmbH, Munich, Germany) to a #50. Longitudinally sectioned halves of the roots were obtained and washed with NaOCl 4%, EDTA 17% and 5% sodium thiosulfate, and sterilized by autoclaving for 15 minutes at 121°C. A multi-species biofilm broth was developed with three strains of bacteria under laboratory conditions: Enterococcus faecalis ATTC 29212, Eikenella corrodens ATTC 23834, Streptococcus anginosus ATTC 33397. Roots were autoclaved and transferred to the broth for 4 days and then were subjected to either disinfection with sodium hypochlorite 4% and XP-endo Finisher (FKG Dentaire, La Chaux-de-Fonds, Switzerland) or chlorhexidine 2% with and without activation with XP-endo Finisher (FKG Dentaire, La Chaux-de-Fonds, Switzerland)., Results: The evaluations of the biofilm elimination showed results that indicate that the 4% sodium hypochlorite group with positive pressure irrigation presented significant differences with the group that had irrigation with sodium hypochlorite activated with XP-endo Finisher and the chlorhexidine groups to 2% ( P <0.05)., Conclusions: Chlorhexidine 2% activated with the XP-endo Finisher does not exert elimination or improved cleaning effect on the multi-species biofilm. Activation of sodium hypochlorite 4% improved the elimination of the multi-species biofilm. Key words: Biofilm, multispecies, chlorhexidine, sodium hypochlorite., Competing Interests: Conflict of interest statement:The authors have declared that no conflict of interest exist., (Copyright: © 2019 Medicina Oral S.L.)