Evaluation of the Cytotoxic Behavior of Fungal Extracellular Synthesized Ag Nanoparticles Using Confocal Laser Scanning Microscope.

Silver nanoparticles have been synthesized by subjecting a reaction medium to a Fusarium oxysporum biomass at 28 °C for 96 h. The biosynthesized Ag nanoparticles were characterized on the basis of their anticipated peak at 405 nm using UV-Vis-NIR spectroscopy. Structural confirmation was evident from the characteristic X-ray diffraction (XRD) pattern, high-resolution transmission electron Microscopy (HRTEM) and the particle size analyzer. The Ag nanoparticles were of dimension 40 ± 5 nm and spherical in shape. The study mainly focused on using the confocal laser scanning microscope (CLSM) to examine the cytotoxic activities of fungal synthesized Ag nanoparticles on a human breast carcinoma cell line MCF7 cell, which featured remarkable vacuolation, thus indicating a potent cytotoxic activity.

Todd's Paresis in Acute Mild Head Trauma.

We present the case of an adult male who sustained Todd's paresis after a traumatically induced seizure in a patient with an isolated facial injury. The precipitating event was head trauma from a golf club. The patient had no previous history of seizures and went on to make a complete neurologic recovery with no cerebral pathology noted. A literature review suggests that Todd's paresis after trauma is very rare as opposed to occurring in the medical or long-term brain injury settings. Although the authors acknowledge that it may occur in trauma, the awareness within the prehospital setting is sufficiently rare for this case report to be of interest to prehospital clinicians; it is important prehospital clinicians are aware of this condition.

Biological Screening of Newly Synthesized BIAN N-Heterocyclic Gold Carbene Complexes in Zebrafish Embryos.

N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10-12 h. One hundred percent mortality was observed at concentrations≥50 µM. At sub-lethal concentrations (10-30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%-40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules.

Sterically directed functionalization of the redox-active bis(imino)acenaphthene ligand class: an experimental and theoretical investigation.

The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N-C-C-N fragment of the Ar-BIAN ligand, functionalization can be directed to proceed either via a radical backbone dearomatization or a nucleophilic imine C-alkylation pathway. The structures of the Ar-BIAN derivatives 14-19 were determined by means of single-crystal X-ray diffraction. The reaction pathways involved in Ar-BIAN functionalization were monitored by means of EPR spectroscopy. The experimental results and observations were examined in conjunction with DFT-D calculations in order to explain the driving forces that direct the pathways leading to Ar-BIAN functionalization.

Trends in use of intraosseous and intravenous access in out-of-hospital cardiac arrest across English ambulance services: A registry-based, cohort study.

INTRODUCTION: The optimum route for drug administration in cardiac arrest is unclear. Recent data suggest that use of the intraosseous route may be increasing. This study aimed to explore changes over time in use of the intraosseous and intravenous drug routes in out-of-hospital cardiac arrest in England. METHODS: We extracted data from the UK Out-of-Hospital Cardiac Arrest Outcomes registry. We included adult out-of-hospital cardiac arrest patients between 2015-2020 who were treated by an English Emergency Medical Service that submitted vascular access route data to the registry. The primary outcome was any use of the intraosseous route during cardiac arrest. We used logistic regression models to describe the association between time (calendar month) and intraosseous use. RESULTS: We identified 75,343 adults in cardiac arrest treated by seven Emergency Medical Service systems between January 2015 and December 2020. The median age was 72 years, 64% were male and 23% presented in a shockable rhythm. Over the study period, the percentage of patients receiving intraosseous access increased from 22.8% in 2015 to 42.5% in 2020. For each study-month, the odds of receiving any intraosseous access increased by 1.019 (95% confidence interval 1.019 to 1.020, p < 0.001). This observed effect was consistent across sensitivity analyses. We observed a corresponding decrease in use of intravenous access. CONCLUSION: In England, the use of intraosseous access in out-of-hospital cardiac arrest has progressively increased over time. There is an urgent need for randomised controlled trials to evaluate the clinical effectiveness of the different vascular access routes in cardiac arrest.

Unique radical dearomatization and two-electron reduction of a redox-active ligand.

The syntheses and characterizations of [Li(4)][(1,2-di-(tert-butyl)-dpp-BIAN)(2)] (7), (1,2-di-(tert-butyl)-dpp-BIAN) (8), and (1-(tert-butyl)-2-OH-dpp-BIAN) (9) are described. Compound 7 was formed via a radical dearomatization, two-electron reduction pathway that was accompanied by vicinal di-tert-butylation of the BIAN ligand backbone. Oxidation of 7 afforded a dearomatized vicinal di-tert-butyl substituted BIAN ligand (8). An analogous dearomatized vicinal tert-butyl-hydroxy substituted BIAN ligand (9) was also isolated in the course of mechanistic studies related to the formation of 7.

Tetrakis(imino)pyracene complexes exhibiting multielectron redox processes.

The differences in redox behavior of the monofunctional bis(imino)acenaphthene (BIAN) and bifunctional tetrakis(imino)pyracene (TIP) ligands have been explored by treatment of the latter with PI(3), TeI(4), or BI(3). These reactions result in the formation of products involving the transfer of three or four electrons. Accompanying DFT calculations reveal that in each case the extent of electron transfer from each p-block element into the TIP ligand is dependent upon the element-TIP bonding interactions.

Synthesis and characterization of a p-type boron arsenide photoelectrode.

A p-type boron arsenide photoelectrode was prepared from a material consisting of a thin layer of boron arsenide on a boron substrate. The structure of the material was identified using X-ray diffraction and scanning electron microscopy, and the surface composition was determined by means of X-ray photoelectron spectroscopy. The electrode was found to be photoactive under both visible light and UV-vis irradiation and displayed a photocurrent of ~0.1 mA/cm(2) under UV-vis irradiation at an applied potential of -0.25 V vs Ag/AgCl. Mott-Schottky plots for this boron arsenide electrode displayed an estimated flat-band potential near the onset photopotential. The estimated indirect band gap, as determined from incident photon-to-electron conversion efficiency plots, is 1.46 ± 0.02 eV.

Recommendation for changes to the guidelines of trauma patients with potential spinal injury within a regional UK ambulance trust.

Background: Spinal assessment and immobilisation has been a topic of debate for many years where, despite an emerging evidence base and the delivery of new guidance overseas, little has changed within UK pre-hospital practice. Since 2018, South East Coast Ambulance Service NHS Foundation Trust has spent time working with local trauma networks and expertise from within the region and international colleagues to develop a set of C-spine assessment and immobilisation guidelines that reflect the current best available international evidence and significant changes in international pre-hospital practice from settings such as Scandinavia and Australasia. Methods: A specialist group was commissioned to review the topic of pre-hospital spinal immobilisation and explore potential for evidence-based improvement. In conjunction with local trauma networks, subject matter experts and a thorough review of recent literature, a series of recommendations were made in order to improve spinal care within the authoring trust. Results: Seven recommendations were made, and an updated set of guidelines produced. These included the removal of semi-rigid collars from pre-hospital spinal immobilisation; the creation of two tiers of patients to ensure that the high-risk and low-risk populations are considered separately and an accompanying decision tool to safeguard both cohorts; an increased emphasis on the risk of spinal injury in the frail and older patient; an emphasis on spinal motion restriction rather than rigid immobilisation; an increased emphasis on self-extrication; and the use of a marker for emergency departments. Summary: An updated set of guidance has been produced using a combination of specialist and expert opinion alongside a literature review with close involvement of key stakeholders, both public and professional. The new guidance helps to ensure a patient-centred approach where each person is considered an individual with their risk of injury and management measures tailored to their specific needs.

Critical care paramedics' experiences of performing an emergency scalpel cricothyroidotomy: a qualitative study.

Introduction: A scalpel cricothyroidotomy or front of neck access (FONA) is a rarely performed part of airway management for when other steps have failed and the patient cannot be intubated or ventilated. Increasingly advanced and specialist paramedics are being trained to perform this procedure within the pre-hospital environment. Methods: Advanced and specialist paramedics within a UK ambulance service that had performed a FONA were invited to participate in this qualitative research. Semi-structured interviews were used to gather information on the participants' experiences. This information underwent thematic analysis to develop codes which were then grouped into themes. Results: Seven participants were interviewed between December 2020 and January 2021. Three main themes were identified: the procedure, isolation and training. The main complications described were bleeding in excess of expectations, moving structures, surgical emphysema and a false track. Conclusion: Complications appeared common; training to perform a FONA should include complications and an approach to their management similar to other airway management procedures. Isolation was a common theme within this study, however remote support from a peer appeared beneficial.

A recyclable, self-supported organocatalyst based on a poly(N-heterocyclic carbene).

We report the synthesis and catalytic activity of a polymeric imidazolium salt. In contrast to the well-known resin-supported N-heterocyclic carbenes (NHCs), the material described herein affords a polymer with NHCs orthogonally positioned along a main chain upon generation in situ. The unique structural characteristics of the corresponding poly(NHC)s enabled the materials to display catalytic activities that were similar or superior to those displayed by monomeric analogues. Moreover, the new catalyst was successfully recovered and reused with minimal loss of performance over several cycles.

Lanthanide-based coordination polymers assembled from derivatives of 3,5-dihydroxy benzoates: syntheses, crystal structures, and photophysical properties.

Two new aromatic carboxylic acids, namely, 3,5-bis(benzyloxy)benzoic acid (HL1) and 3,5-bis(pyridine-2-ylmethoxy)benzoic acid (HL2), have been prepared by replacing the hydroxyl hydrogens of 3,5-dihydroxy benzoic acid with benzyl and pyridyl moieties, respectively. The anions derived from HL1 and HL2 have been used for the support of a series of lanthanide coordination compounds [Eu(3+) = 1-2; Tb(3+) = 3-4; Gd(3+) = 5-6]. The new lanthanide complexes have been characterized on the basis of a variety of spectroscopic techniques in conjunction with an assessment of their photophysical properties. Lanthanide complexes 2, 4, and 6, which were synthesized from 3,5-bis(pyridine-2-ylmethoxy)benzoic acid, were structurally authenticated by single-crystal X-ray diffraction. All three complexes were found to exist as infinite one-dimensional (1-D) coordination polymers with the general formula {[Ln(L2)(3)(H(2)O)(2)]·xH(2)O}(n). Scrutiny of the packing diagrams for 2, 4, and 6 revealed the existence of interesting two-dimensional molecular arrays held together by intermolecular hydrogen-bonding interactions. Furthermore, the coordinated benzoate ligands serve as efficient light harvesting chromophores. In the cases of 1-4, the lowest energy maxima fall in the range 280-340 nm [molar absorption coefficient (ε) = (0.39-1.01) × 10(4) M(-1) cm(-1)]. Moreover, the Tb(3+) complexes 3 and 4 exhibit bright green luminescence efficiencies in the solid state (Φ(overall) = 60% for 3; 27% for 4) and possess longer excited state lifetimes than the other complexes (τ = 1.16 ms for 3; 1.38 ms for 4). In contrast to the foregoing, the Eu(3+) complexes 1 and 2 feature poor luminescence efficiencies.

Syntheses, structures and antimicrobial activities of bis(imino)acenaphthene (BIAN) imidazolium salts.

The syntheses of four new bis(imino)acenaphthene (BIAN) imidazolium chlorides are reported, three of which have been structurally characterized. The synthesis of a new, structurally authenticated BIAN ligand is also described. We report the results of the use of these BIAN imidazolium salts as antimicrobials against the pathogens S. aureus, B. subtilis, E. coli and P. aeruginosa. The antimicrobial efficacies were particularly high for the N-(2,6-diisopropylphenyl)- and N-(mesityl)-substituted BIAN imidazolium salts (MIC values < 0.6 µg/mL).

Antimicrobial properties of some bis(iminoacenaphthene (BIAN)-supported N-heterocyclic carbene complexes of silver and gold.

The AgCl, AgOAc, AuCl, and AuOAc complexes of the new bis(imino)acenaphthene(BIAN)-supported N-heterocyclic carbene ligand and the precursor imidazolium salt have been investigated with respect to their antimicrobial activities against Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Psudomonas aeruginosa. The most active antimicrobial is the precursor imidazolium salt, which has a minimum inhibitory concentration (MIC) value of <40 µg/mL. The MIC values for the silver complexes IPr(BIAN)AgCl and IPr(BIAN)AgOAc against Gram-positive S. aureus are comparable to that for AgNO3, while those against Gram-negative E. coli and P.aeroginosa are significantly larger. Similar behavior was evident for the gold acetate complex IPr(BIAN)AuOAc. However, in the case of the gold chloride analogue, the MIC values are virtually identical for both the Gram-positive and the Gram-negative bacteria.

The Epidemiology and Effectiveness of Synchronized Cardioversion in a UK Prehospital Setting: A Retrospective Cross-Sectional Study.

BACKGROUND: Synchronized cardioversion is an internationally accepted standard therapy for unstable tachyarrhythmias, but it is conventionally an in-hospital physician-led intervention. Increasingly, it is being brought forward into the prehospital setting as part of a specialist paramedic scope of practice; however, very little literature exists regarding the epidemiology or efficacy in this setting. METHODS: All patients receiving cardioversion within a United Kingdom (UK) ambulance service were identified using an electronic database. The period of inclusion was March 1, 2017 through October 31, 2020. These data were then interrogated to provide demographic, physiological, and efficacy data, and then a sub-group was created to identify those who presented with a primary arrhythmia (as opposed to post-cardiac arrest). RESULTS: From a total of 93 patients, prehospital synchronized cardioversion successfully terminated the tachyarrhythmia in 96% of patients presenting with a primary arrhythmia (85% in the allcomers group) with a predominance towards males (82% of patients) and an average age of 67 years. Hypotension and reduced level of consciousness were the most commonly documented unstable features (84.4% and 44.4%). CONCLUSION: Cardioversion within a paramedic-led service results in efficacy rates of 96% in patients presenting with a primary tachyarrhythmia. This is a similar efficacy rate to traditional doctor-led therapies. Demographic data show that males make up over 80% of the patient population, in keeping with previously published work across the spectrum of cardiac interventions.

Design, synthesis, and study of main chain poly(n-heterocyclic carbene) complexes: applications in electrochromic devices.

A series of poly(N-heterocyclic carbene) complexes in which the carbene functionalities are orthogonally connected to the main chains of the respective polymers have been synthesized via oxidative electropolymerization of various bis(bithiophene)-substituted monomers with appended transition metal or main group entities (M = Ir, Au, Ag, or S). The polymers were characterized using a range of electrochemical, X-ray photoelectron spectroscopy, UV-vis spectroscopy, profilometry, and four-point probe conductivity measurements. Most of the polymers exhibited an intense absorbance wave at 700 nm under oxidative conditions which was attributable to the formation of polarons along the main chains. The iridium-containing thin film poly(8) was found to possess a significant NIR absorbance at 1100 nm in which the metal moiety effectively functioned as an electron sink. Electrochemical analyses of the polymer thin films revealed that they exhibited highly reversible electrochromic phenomena.

Synthesis, crystal structure, and photoluminescence of homodinuclear lanthanide 4-(dibenzylamino)benzoate complexes.

Three new binuclear lanthanide complexes of general formula [Ln(2)(L)(6)(H(2)O)(4)] (Ln = Tb (1), Eu (2), and Gd (3)) supported by the novel aromatic carboxylate ligand 4-(dibenzylamino)benzoic acid (HL) have been synthesized. Complexes 1 and 2 were structurally characterized by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic space group P(1), and their molecular structures consist of homodinuclear species that are bridged by two oxygen atoms from two carboxylate ligands via different coordination modes. The discrete bridged dimer of 1 is centrosymmetric and features 8-coordinate terbium atoms, each of which adopts a distorted square-antiprismatic geometry. Both coordination spheres comprise two eta(2)-chelating benzoates, two mu-eta(1):eta(1)-carboxylate interactions from the bridging benzoates, and two water molecules. By contrast, in complex 2, the Eu(3+) ion coordination environment is best described as a distorted tricapped-trigonal prism, each europium ion being coordinated to three eta(2)-chelating benzoate ligands and two water molecules. One of the eta(2)-carboxylate ligands is involved in a further interaction with an adjacent metal, thus rendering the overall binding mode bridging tridentate, mu-eta(2):eta(1). Scrutiny of the packing diagrams for 1 and 2 revealed the existence of a one-dimensional molecular array that is held together by intermolecular hydrogen-bonding interactions. The Tb(3+) complex 1 exhibits high green luminescence efficiency in the solid state with a quantum yield of 82%. On the other hand, poor luminescence efficiency has been noted for the Eu(3+)-4-(dibenzylamino)benzoate complex.

Highly luminescent poly(methyl methacrylate)-incorporated europium complex supported by a carbazole-based fluorinated ß-diketonate ligand and a 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide co-ligand.

A novel efficient antenna complex of Eu(3+) [Eu(CPFHP)(3)(DDXPO)] supported by a highly fluorinated carbazole-substituted ß-diketonate ligand, namely, 1-(9H-carbazol-2-yl)-4,4,5,5,5-pentafluoro-3-hydroxypent-2-en-1-one (CPFHP) and the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide (DDXPO) ancillary ligand, has been synthesized, structurally characterized, and its photoluminescent behavior examined. The single-crystal X-ray diffraction analysis of Eu(CPFHP)(3)(DDXPO) revealed that this complex is mononuclear, and that the central Eu(3+) ion is surrounded by eight oxygen atoms, six of which are provided by the three bidentate ß-diketonate ligands. The remaining two oxygen atoms are furnished by the chelating phosphine oxide ligand. The coordination polyhedron is best described as that of a distorted square antiprism. The photophysical properties of Eu(CPFHP)(3)(DDXPO) benefit from adequate protection of the metal by the ligands with respect to non-radiative deactivation as well as an efficient ligand-to-metal energy transfer process which exceeds 66% in chloroform solution with a quantum yield of 47%. As an integral part of this work, the synthesis, characterization, and luminescent properties of poly(methyl methacrylate) (PMMA) polymer films doped with Eu(CPFHP)(3)(DDXPO) are also reported. The luminescent efficiencies of the doped films (photoluminescence quantum yields 79-84%) are dramatically enhanced in comparison with that of the precursor complex. The new luminescent PMMA-doped Eu(CPFHP)(3)(DDXPO) complex therefore shows considerable promise for polymer light-emitting diode and active polymer optical fiber applications.

Electropolymerization of an N-heterocyclic carbene-gold(I) complex.

We report the first example of a polymer in which each monomer contains an N-heterocyclic carbene (NHC) orthogonally connected to its main chain. A polymerizable imidazolylidene-AuCl complex containing pendant bithiophene moieties was prepared in a high-yield multistep procedure. Oxidative electropolymerization of this monomer afforded the desired polymer, (Au[NHC]Cl)(n), which was characterized via electrochemical studies as well as X-ray photoelectron and UV-vis spectroscopy.

Presence of a pre-hospital enhanced care team reduces on scene time and improves triage compliance for stab trauma.

BACKGROUND: A reduction in pre-hospital scene time for patients with penetrating trauma is associated with reduced mortality, when combined with appropriate hospital triage. This study investigated the relationship between presence of pre-hospital enhanced care teams (ECT) (Critical Care Paramedics (CCPS) or Helicopter Emergency Medical Service (HEMS)), on the scene time and triage compliance, of penetrating trauma patients in a UK ambulance service. The primary outcome was whether scene time reduces when an ECT is present. A secondary outcome was whether the presence of an ECT improved compliance with the trust's Major Trauma Decision Tree (MTDT). METHODS: All suspected penetrating trauma incidents involving a patient's torso were identified from the Trust's computer-aided dispatch (CAD) system between 31st March 2017 and 1st April 2018. Only patients who sustained central penetrating trauma were included. Any incidents involving firearms were excluded due to the prolonged times that can be involved when waiting for specialist police units. Data relevant to scene time for each eligible incident were retrieved, along with the presence or absence of an ECT. The results were analysed to identify trends in the scene times and compliance with the MTDT. RESULTS: One hundred seventy-one patients met the inclusion criteria, with 165 having complete data. The presence of an ECT improved the median on-scene time in central stabbing by 38% (29m50s vs. 19m0s, p = 0.03). The compliance with the trust's MTDT increased dramatically when an ECT is present (81% vs. 37%, odds ratio 7.59, 95% CI, 3.70-15.37, p < 0.0001). CONCLUSIONS: The presence of an ECT at a central stabbing incident significantly improved the scene time and triage compliance with a MTDT. Ambulance services should consider routine activation of ECTs to such incidents, with subsequent service evaluation to monitor patient outcomes. Ambulance services should continue to strive to reduce scene times in the context of central penetrating trauma.