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The experimental realization of p-orbital systems is desirable because p-orbital lattices have been proposed theoretically to host strongly correlated electrons that exhibit exotic quantum phases. Here, we synthesize a two-dimensional Fe-coordinated bimolecular metal-organic framework which constitutes a honeycomb lattice of 1,4,5,8,9,12-hexaazatriphenylene molecules and a Kagome lattice of 5,15-di(4-pyridyl)-10,20-diphenylporphyrin molecules on a Au(111) substrate. Density-functional theory calculations show that the framework features multiple well-separated spin-polarized Kagome bands, namely Dirac cone bands and Chern flat bands, near the Fermi level. Using tight-binding modelling, we reveal that these bands are originated from two effects: the low-lying molecular orbitals that exhibit p-orbital characteristics and the honeycomb-Kagome lattice. This study demonstrates that p-orbital Kagome bands can be realized in metal-organic frameworks by using molecules with molecular orbitals of p-orbital like symmetry.

Creating conjugated macrocycles has attracted extensive research interest because their unique chemical and physical properties, such as conformational flexibility, intrinsic inner cavities and aromaticity/antiaromaticity, make these systems appealing building blocks for functional supramolecular materials. Here, we report the synthesis of four-, six- and eight-membered tetraphenylethylene (TPE)-based macrocycles on Ag(111) via on-surface Ullmann coupling reactions. The as-synthesized macrocycles are spontaneously segregated on the surface and self-assemble as large-area two-dimensional mono-component supramolecular crystals, as characterized by scanning tunneling microscopy (STM). We propose that the synthesis benefits from the conformational flexibility of the TPE backbone in distinctive multi-step reaction pathways. This study opens up opportunities for exploring the photophysical properties of TPE-based macrocycles.

Two-dimensional (2D) semiconducting monolayers such as transition metal dichalcogenides (TMDs) are promising channel materials to extend Moore’s Law in advanced electronics. Synthetic TMD layers from chemical vapor deposition (CVD) are scalable for fabrication but notorious for their high defect densities. Therefore, innovative endeavors on growth reaction to enhance their quality are urgently needed. Here, we report that the hydroxide W species, an extremely pure vapor phase metal precursor form, is very efficient for sulfurization, leading to about one order of magnitude lower defect density compared to those from conventional CVD methods. The field-effect transistor (FET) devices based on the proposed growth reach a peak electron mobility ~200 cm2/Vs (~800 cm2/Vs) at room temperature (15 K), comparable to those from exfoliated flakes. The FET device with a channel length of 100 nm displays a high on-state current of ~400 µA/µm, encouraging the industrialization of 2D materials.

Background Neuraxial procedures are commonly performed for therapeutic and diagnostic indications. Currently, they are typically performed via palpation-guided surface landmark. We devised a novel intelligent image processing system that identifies spinal landmarks using ultrasound images. Our primary aim was to evaluate the first attempt success rate of spinal anesthesia using landmarks obtained from the automated spinal landmark identification technique. Methods In this prospective cohort study, we recruited 100 patients who required spinal anesthesia for surgical procedures. The video from ultrasound scan image of the L3/4 interspinous space in the longitudinal view and the posterior complex in the transverse view were recorded. The demographic and clinical characteristics were collected and analyzed based on the success rates of the spinal insertion. Results Success rate (95%CI) for dural puncture at first attempt was 92.0% (85.0–95.9%). Median time to detection of posterior complex was 45.0 [IQR: 21.9, 77.3] secs. There is good correlation observed between the program-recorded depth and the clinician-measured depth to the posterior complex (r = 0.94). Conclusions The high success rate and short time taken to obtain the surface landmark with this novel automated ultrasound guided technique could be useful to clinicians to utilise ultrasound guided neuraxial techniques with confidence to identify the anatomical landmarks on the ultrasound scans. Future research would be to define the use in more complex patients during the administration of neuraxial blocks. Trial registration This study was retrospectively registered on clinicaltrials.gov registry (NCT03535155) on 24 May 2018.

The recognition of quasicrystals, which exhibit long-range order but lack translational symmetry, represented both the introduction of a new class of materials and a transformative breakthrough in crystallography. Concomitant with the exploration of quasicrystallinity, metal-organic architectures emerged as promising and versatile systems with significant application potential. Their building principles have been studied extensively and become manifest in a multitude of intricate amorphous and crystalline phases. To date, however, indications for quasicrystalline order have been elusive in metal-organic coordination networks (MOCNs). Here we employ rare-earth-directed assembly to construct a two-dimensional tiling with quasicrystalline characteristics at a well-defined gold substrate. By careful stoichiometry control over europium centres and functional linkers, we produced a porous network, including the simultaneous expression of four-fold, five-fold and six-fold vertices. The pertaining features were directly inspected by scanning tunnelling microscopy, and the molecule-europium reticulation was recognized as square-triangle tessellation with dodecagonal symmetry. Our findings introduce quasicrystallinity in surface-confined MOCNs with a nanoporous structure and anticipate functionalities that arise from quasicrystalline ordering of the coordinative spheres.

Background Epidural catheter re-siting in parturients receiving labour epidural analgesia is distressing to the parturient and places them at increased complications from a repeat procedure. The aim of this study was to develop and validate a clinical risk factor model to predict the incidence of epidural catheter re-siting in labour analgesia. Methods The data from parturients that received labour epidural analgesia in our centre during 2014–2015 was used to develop a predictive model for epidural catheter re-siting during labour analgesia. Multivariate logistic regression analysis was used to identify factors that were predictive of epidural catheter re-siting. The forward, backward and stepwise variable selection methods were applied to build a predictive model, which was internally validated. The final multivariate model was externally validated with the data collected from 10,170 parturients during 2012–2013 in our centre. Results Ninety-three (0.88%) parturients in 2014–2015 required re-siting of their epidural catheter. The training data set included 7439 paturients in 2014–2015. A higher incidence of breakthrough pain (OR = 4.42), increasing age (OR = 1.07), an increased pain score post-epidural catheter insertion (OR = 1.35) and problems such as inability to obtain cerebrospinal fluid in combined spinal epidural technique (OR = 2.06) and venous puncture (OR = 1.70) were found to be significantly predictive of epidural catheter re-siting, while spontaneous onset of labour (OR = 0.31) was found to be protective. The predictive model was validated internally on a further 3189 paturients from the data of 2014–2015 and externally on 10,170 paturients from the data of 2012–2013. Predictive accuracy of the model based on C-statistic were 0.89 (0.86, 0.93) and 0.92 (0.88, 0.97) for training and internal validation data respectively. Similarly, predictive accuracy in terms of C-statistic was 0.89 (0.86, 0.92) based on 2012–2013 data. Conclusion Our predictive model of epidural re-siting in parturients receiving labour epidural analgesia could provide timely identification of high-risk paturients required epidural re-siting.

The LMA Protector™ is the latest CE marked single use supraglottic airway device. This airway device provides access and functional separation of the respiratory and digestive tracts. There are two ports (male, female ports) to provide suction in the laryngeal region and insertion of the gastric tube. The aim of our study is to assess the ease of use, airway quality, device positioning, airway leak and complications associated with initial clinical experience in LMA Protector™ usage. This is an initial investigation of LMA Protector™ airway device. We conducted a preliminary assessment in the anaesthetised women who underwent minor gynaecological procedures with spontaneous ventilation in order to evaluate the performance of the airway device. Insertion was successful on first and second attempts in 23 (88.5%) and 3 (11.5%) respectively. Median [IQR (range)] insertion time was 19 [17-21(14-58)] seconds. Airway leak pressure was 25.5 [23-29(21-30] cmH2O. On fibreoptic examination via the device, vocal cords were visible in all 26 patients. There were no alternative airway use or airway manipulations required during maintenance of anaesthesia. Six patients had sore throat 24 h after procedures and there was no dysphagia or hoarseness. This pilot study of the LMA protector shows that the device is easily inserted with fast insertion time, providing a reliable and adequate airway seal. Clinicaltrials.gov Registration NCT02531256 . Retrospectively registered on August 21, 2015.

The controlled formation of non-covalent bonds (H-bonding, metal–ligand interactions) is the key ingredient for the fabrication of supramolecular architectures and nanostructures. Upon deposition of molecular building blocks at well-defined surfaces, this issue can be directly addressed. Scanning tunneling microscopy observations are presented, which provide insight into the interaction of functional groups on metal substrates at the molecular level. In particular, carboxylic acids were employed: (4-[(pyrid-4-yl-ethynyl)]-benzoic acid (PEBA), 4-[trans-2-(pyrid-4-yl-vinyl)]-benzoic acid (PVBA) and trimesic acid (1,3,5-benzenetricarboxylic acid, TMA), which could be stabilized in a flat geometry at the surface. By choosing the appropriate substrate material and symmetry, the sensitive balance of intermolecular and molecule–substrate interactions can be tuned to obtain well-defined supramolecular architectures and nanostructures. The head-to-tail hydrogen bonding of the related rod-like species PEBA and PVBA stabilizes molecular rows on Ag(111). The subtle difference in the molecular geometries is reflected in the lateral ordering: While 2-D islanding is encountered with PEBA, 1-D nanogratings of supramolecular chiral H-bonded twin chains evolve for PVBA. The threefold symmetry of TMA in conjunction with the self-complementarity of its exodentate groups accounts for the formation of H-bonded honeycomb networks on Cu(100) at low temperatures. Metal–ligand interactions were probed with PVBA and TMA at Cu surfaces at ambient temperature. Deprotonation of the carboxyl moiety takes place, which readily interacts with Cu adatoms evaporated from step edges. This leads to a head-to-head pairing of PVBA on Cu(111) and cloverleaf-shaped Cu–TMA coordination compounds on Cu(001).

The thermal stability of carbon nitride films, deposited by reactive direct current magnetron sputtering in N2 discharge, was studied for postdeposition annealing temperatures TA up to 1000 °C. Films were grown at temperatures of 100 °C (amorphous structure) and 350 and 550 °C (fullerenelike structure) and were analyzed with respect to thickness, composition, microstructure, bonding structure, and mechanical properties as a function of TA and annealing time. All properties investigated were found to be stable for annealing up to 300 °C for long times (>48 h). For higher TA, nitrogen is lost from the films and graphitization takes place. At TA = 500 °C the graphitization process takes up to 48 h while at TA = 900 °C it takes less than 2 min. A comparison on the evolution of x-ray photoelectron spectroscopy, electron energy loss spectroscopy and Raman spectra during annealing shows that for TA > 800 °C, preferentially pyridinelike N and –C≡N is lost from the films, mainly in the form of molecular N2 and C2N2, while N substituted in graphite is preserved the longest in the structure. Films deposited at the higher temperature exhibit better thermal stability, but annealing at temperatures a few hundred degrees Celsius above the deposition temperature for long times is always detrimental for the mechanical properties of the films.