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The Oxalert EPO is a wearable device that detects and alerts patients to hypoxemia. In a pre-planned pilot trial, we estimated the effect of continuous saturation monitoring with patient alerts on in-hospital and post-discharge saturation; we further assessed the feasibility of the intervention.Noncardiac surgical patients were randomized to either the Oxalert with patient alerts (Monitor+Alert, N=25) or the Oxalert without patient alerts (Monitor Only, N=24). Monitoring continued during hospitalization for up to six days and for 24 hours after hospital discharge. Patients in each group were compared on time-weighted average SpOWe enrolled ≥2 patients per week, for a total of 49 patients in whom recording were obtained for a median [quartiles] of 91 [85, 95] percent of the time in-hospital. In-hospital, time-weighted average SpOThe Oxalert system was well tolerated in both groups and enrollment was strong. Patients randomized to active Oxalert systems experienced half as many postoperative desaturation events while hospitalized, although the difference was not statistically significant in this small pilot trial. In contrast, the Oxalert system did not reduce post-discharge desaturation. A full trial of in-hospital desaturation alerts thus seems warranted. The trial was registered at ClincialTrial.gov (NCT04453722). This article is protected by copyright. All rights reserved.

Myocardial injury due to ischaemia within 30 days of non-cardiac surgery is prognostically relevant. We aimed to determine the discrimination, calibration, accuracy, sensitivity and specificity of single-layer and multiple-layer neural networks for myocardial injury and death to 30 postoperative days. We analysed data from 24,589 participants in the vascular events in noncardiac surgery patients cohort evaluation study. Validation was performed on a randomly selected subset of the study population. Discrimination for myocardial injury by single-layer vs. multiple-layer models generated areas (95%CI) under the receiver operating characteristic curve of: 0.70 (0.69-0.72) vs. 0.71 (0.70-0.73) with variables available before surgical referral, p < 0.001; 0.73 (0.72-0.75) vs. 0.75 (0.74-0.76) with additional variables available on admission, but before surgery, p < 0.001; and 0.76 (0.75-0.77) vs. 0.77 (0.76-0.78) with the addition of subsequent variables, p < 0.001. Discrimination for death by single-layer vs. multiple-layer models generated areas (95%CI) under the receiver operating characteristic curve of: 0.71 (0.66-0.76) vs. 0.74 (0.71-0.77) with variables available before surgical referral, p = 0.04; 0.78 (0.73-0.82) vs. 0.83 (0.79-0.86) with additional variables available on admission but before surgery, p = 0.01; and 0.87 (0.83-0.89) vs. 0.87 (0.85-0.90) with the addition of subsequent variables, p = 0.52. The accuracy of the multiple-layer model for myocardial injury and death with all variables was 70% and 89%, respectively.

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its Ni(II)-complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole and subsequent reaction with pentafluorobenzaldehyde, afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted Ni(II) insertion with Ni(OAc)2•4H2O resulted an ESR active, Ni(II) bipyricorrole radical complex, which is converted to stable cationic Ni(II) complex upon treatment with [(Et3O)+(SbCl6)-]. Both complexes were characterized by 1H- and 13C-NMR, UV-vis spectroscopy and single crystal X-ray diffraction analysis. The Ni(II) bipyricorrole radical complex is converted to cationic Ni(II) complex by single electron reduction using cobaltocene. Both cationic Ni(II) complex and radical Ni(II) complex exhibit ligand-centered redox behavior while the Ni(II) remains in the +2 oxidation state.

A pair of meso-unsubstituted expanded carbaporphyrins containing two carbazole moieties were prepared in high isolated yields (82 and 76 %, respectively). The two macrocycles, namely 3 and 4, differ with respect to their substitution at the carbazole N-atoms i. e. by H and i-Bu, respectively. As prepared in their free-base forms, macrocycles 3 and 4 adopt figure-of-eight conformations and are best characterized as 40 π-electron, non-aromatic species possessing a decaphyrin(1.1.0.0.0.1.1.0.0.0) skeleton. Protonation of 3 with either trifluoroacetic acid (TFA) or perchloric acid (HClO4 ) produces a parallelogram-shaped structure. A similar structure is produced when N-functionalized system 4 is treated with TFA. In contrast, protonation of 4 with HClO4 leads it to adopt a twisted Mobius strip-like structure in the solid state, thus allowing access to three distinct conformational states as a function of the conditions.

A non-aromatic expanded carbaporphyrinoid, incorporating two built-in 2,7-pyrenylene moieties was synthesized. The intrinsically labile topographic structure was demonstrated by proton-triggered conformational changes between the figure-of-eight and quasi-Möbius conformers. Upon treatment with Pd(OAc) 2 , the reaction produces two bis-Pd II complexes with distinct coordination modes. Metal coordination serves to fix the oligopyrrolic macrocyclic frame-works with the net result that both bis-Pd II complexes could be resolved by chiral high-performance liquid chromatography (HPLC). The isolated enantiomers showed considerable configurational stability and persistent chiroptical properties as evidenced by the intense response in the circular dichroism (CD) spectra from 300-850 nm and the record high absorption dissymmetry factors ( g abs of up to 0.038) seen in the near-infrared spectral region. In addition, the mutual interconversion of the enantiomers was found to be stereospecific and to favor the more stable isomers in the presence of the weakly acidic solvent deuterated chloroform.

Resistance to chemotherapy-induced cell death is a major barrier to effective treatment of solid tumours such as colorectal cancer, CRC. Herein, we present a study aimed at developing a proteomics-based predictor of response to standard-of-care (SoC) chemotherapy in combination with antagonists of IAPs (inhibitors of apoptosis proteins), which have been implicated as mediators of drug resistance in CRC. We quantified the absolute expression of 19 key apoptotic proteins at baseline in a panel of 12 CRC cell lines representative of the genetic diversity seen in this disease to identify which proteins promote resistance or sensitivity to a model IAP antagonist [birinapant (Bir)] alone and in combination with SoC chemotherapy (5FU plus oxaliplatin). Quantitative western blotting demonstrated heterogeneous expression of IAP interactome proteins across the CRC cell line panel, and cell death analyses revealed a widely varied response to Bir/chemotherapy combinations. Baseline protein expression of cIAP1, caspase-8 and RIPK1 expression robustly correlated with response to Bir/chemotherapy combinations. Classifying cell lines into 'responsive', 'intermediate' and 'resistant' groups and using linear discriminant analysis (LDA) enabled the identification of a 12-protein signature that separated responders to Bir/chemotherapy combinations in the CRC cell line panel with 100% accuracy. Moreover, the LDA model was able to predict response accurately when cells were cocultured with Tumour necrosis factor-alpha to mimic a pro-inflammatory tumour microenvironment. Thus, our study provides the starting point for a proteomics-based companion diagnostic that predicts response to IAP antagonist/SoC chemotherapy combinations in CRC.

Published data suggest that the type of general anaesthesia used during surgical resection for cancer may impact on patient long-term outcome. However, robust prospective clinical evidence is essential to guide a change in clinical practice. We explored the feasibility of conducting a randomised controlled trial to investigate the impact of total intravenous anaesthesia with propofol vs. inhalational volatile anaesthesia on postoperative outcomes of patients undergoing major cancer surgery. We undertook a randomised, double-blind feasibility and pilot study of propofol total intravenous anaesthesia or volatile-based maintenance anaesthesia during cancer resection surgery at three tertiary hospitals in Australia and the USA. Patients were randomly allocated to receive propofol total intravenous anaesthesia or volatile-based maintenance anaesthesia. Primary outcomes for this study were successful recruitment to the study and successful delivery of the assigned anaesthetic treatment as per randomisation arm. Of the 217 eligible patients approached, 146 were recruited, a recruitment rate of 67.3% (95%CI 60.6-73.5%). One hundred and forty-five patients adhered to the randomised treatment arm, 99.3% (95%CI 96.2-100%). Intra-operative patient characteristics and postoperative complications were comparable between the two intervention groups. This feasibility and pilot study supports the viability of the protocol for a large, randomised controlled trial to investigate the effect of anaesthesia technique on postoperative cancer outcomes. The volatile anaesthesia and peri-operative outcomes related to cancer (VAPOR-C) study that is planned to follow this feasibility study is an international, multicentre trial with the aim of providing evidence-based guidelines for the anaesthetic management of patients undergoing major cancer surgery.

Access to clean drinking water is a recognized societal need that touches on the health and livelihood of millions of people worldwide. This is providing an incentive to develop new water-treatment technologies. Traditional technologies, while widespread, are usually inefficient at removing organic pollutants from sewage or so-called grey water. Macrocycle-containing covalent polymer networks have begun to attract attention in the context of water treatment owing to the inherent stability provided by the polymer backbones and their ability to capture micropollutant guests as the result of tunable macrocycle-based host-guest interactions. In this Minireview, we summarize recent advances (from 2016 to mid-2020) involving the removal of organic micropollutants from water using macrocycle-containing covalent polymer networks. An overview of future challenges within this subfield is also provided.

Two giant calix[n]phyrin derivatives namely calix[8]- (4) and calix[16]phyrin (5), involving two and four BF2 units, respectively, were prepared through the condensation of the bis-naphthobipyrrolylmethene-BF2 complex (3) with pentafluorobenzaldehyde. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82×105 m-1 cm-1 , respectively) in the near-IR region, which was taken as initial evidence for strong excitonic coupling within these cyclic multi-chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from fluorescence, time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements. Support for these experimental findings came from theoretical studies. Theory and experiment confirmed that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.

BACKGROUND Volatile anesthetics potentially trigger malignant hyperthermia crises in susceptible patients. We therefore aimed to identify preparation procedures for the Draeger Primus that minimize residual concentrations of desflurane and sevoflurane with and without activated charcoal filtration. METHODS A Draeger Primus test workstation was primed with 7% desflurane or 2.5% sevoflurane for 2 hours. Residual anesthetic concentrations were evaluated with five preparation procedures, three fresh gas flow rates, and three distinct applications of activated charcoal filters. Finally, non-exchangeable and autoclaved parts of the workstation were tested for residual emission of volatile anesthetics. Concentrations were measured by multicapillary column-ion mobility spectrometry with limits of detection/quantification being

A series of calix[4]pyrrole-based crosslinked polymer networks designed for iodine capture is reported. These materials were prepared by Sonogashira coupling of α,α,α,α-tetra(4-alkynylphenyl)calix[4]pyrrole with bishalide building blocks with different electronic properties and molecular sizes. Despite their low Brunauer-Emmett-Teller surface areas, iodine vapor adsorption capacities of up to 3.38 g g-1 were seen, a finding ascribed to the presence of a large number of effective sorption sites including macrocyclic π-rich cavities, aryl units, and alkyne groups within the material. One particular system, C[4]P-BTP, was found to be highly effective at iodine capture from water (uptake capacity of 3.24 g g-1 from a concentrated aqueous KI/I2 solution at ambient temperature). Fast capture kinetics (kobs = 7.814 g g-1 min-1) were seen.. Flow-through adsorption experiments revealed that C[4]P-BTP is able to remove 93.2% of iodine from an aqueous source phase at a flow rate of 1 mL min-1.

Ultrasound is increasingly being adopted into anaesthesia and intensive care practice. The range of ultrasound examination has also increased from transoesophageal echocardiography in cardiac surgery and ultrasound-guided nerve blocks and vascular access, to examination of the heart, lungs, abdomen and deep veins. Typically, the use of ultrasound is focused or basic, designed to be performed by the anaesthetist at the patient's bedside in real time to answer clinical questions and to direct therapy. Ultrasound is not performed in isolation, but used to complement clinical evaluation, and accordingly can be considered as 'ultrasound-assisted perioperative evaluation'. Whilst there is good evidence that ultrasound improves diagnostic accuracy and in turn alters management, there are few data examining whether ultrasound leads to improved clinical outcomes. This review will examine multiple uses of perioperative ultrasound with case studies to illustrate potential utility.

Patients with pre-surgery cognitive impairment cannot currently be assessed for cognitive recovery after surgery using the Postoperative Quality of Recovery Scale (PostopQRS), as they would mathematically be scored as recovered. We aimed to validate a novel method to score cognitive recovery in patients with low-baseline cognition, using the number of low-score tests rather than their numerical values. Face validity was demonstrated in 86 participants in whom both the Postoperative Quality of Recovery Scale and an 11-item neuropsychological battery were performed. The Postoperative Quality of Recovery Scale agreed with neuropsychological categorisation of low vs. normal cognition 74% of the time, with all but five incorrectly coded participants deviating by only one neurocognitive test. Cognitive recovery over time was comparable for groups with differing baseline cognitive function, irrespective of whether the Postoperative Quality of Recovery Scale or neuropsychological methods were used. Discriminant validation was demonstrated in a post-hoc analysis of the steroids in cardiac surgery substudy by allocating groups to normal (n = 246) or low-baseline cognition (n = 231) stratified by cognitive recovery on day 1. Recovery was similar for participants with low and normal baseline cognition. Postoperative length of stay was longer in patients with failed cognitive recovery whether they had normal mean (SD) (10.4 (10.0) vs. 8.0 (5.9) days, p = 0.02) or low-baseline cognition (12.0 (11.1) vs. 8.2 (4.7) days, p < 0.01). Overall quality, as well as cognitive, emotive and physiological recovery was independent of baseline cognition. The modified scoring method for the Postoperative Quality of Recovery Scale cognitive domain demonstrates acceptable face and discriminant validity.

LiCl is a classic "hard" ion salt that is present in lithium-rich brines and a key component in end-of-life materials (that is, used lithium-ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Herein, we describe two ditopic calix[4]pyrrole-based ion-pair receptors (2 and 3), that are capable of selectively capturing LiCl. Under solid-liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl/KCl salt mixture containing as little as 1 % LiCl with circa 100 % selectivity, while receptor 3 achieved similar separations when the LiCl level was as low as 200 ppm. Under liquid-liquid extraction conditions using nitrobenzene as the non-aqueous phase, the extraction preference displayed by 2 is KCl>NaCl>LiCl. In contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.