Unusual Regio- and Chemoselectivity in Oxidation of Pyrroles and Indoles Enabled by a Thianthrenium Salt Intermediate.

A dearomative oxidation of pyrroles to Δ-pyrrol-2-ones is described, which employs a sulfoxide as oxidant, in conjunction with a carboxylic acid anhydride and a Brønsted acid additive. 3-substituted pyrroles undergo regioselective oxidation to give the product isomer in which oxygen has been introduced at the more hindered position. Regioselectivity is rationalized by a proposed mechanism that proceeds by initial thianthrenium introduction at the less-hindered pyrrole α-position, followed by distal attack of an oxygen nucleophile and subsequent elimination of thianthrene.

Synthesis of -alkoxycarbonyl Pyrroles from -Substituted Carbamates: A Synthetically Enabling Pyrrole Protection Strategy.

The condensation of readily available -substituted carbamates with 2,5-dimethoxytetrahydrofuran gives -alkoxycarbonyl pyrroles in a single step and in good yield. By this method, several common amine protecting groups can be introduced on the pyrrole nitrogen. With the exception of -Boc, -alkoxycarbonyl groups have seen only minimal use for protection of the pyrrole nitrogen to date.

Influence of Thermal and Flash-Lamp Annealing on the Thermoelectrical Properties of CuZnSnS Nanocrystals Obtained by "Green" Colloidal Synthesis.

The problem with waste heat in solar panels has stimulated research on materials suitable for hybrid solar cells, which combine photovoltaic and thermoelectric properties. One such potential material is CuZnSnS (CZTS). Here, we investigated thin films formed from CZTS nanocrystals obtained by "green" colloidal synthesis.

Raman Spectroscopy and Thermoelectric Characterization of Composite Thin Films of CuZnSnS Nanocrystals Embedded in a Conductive Polymer PEDOT:PSS.

CuZnSnS (CZTS) is an intensively studied potential solar cell absorber and a promising thermoelectric (TE) material. In the form of colloidal nanocrystals (NCs), it is very convenient to form thin films on various substrates. Here, we investigate composites of CZTS NCs with PEDOT:PSS, a widely used photovoltaics polymer.

Persistent azulene α-carbocations: synthesis from aldehydes, spectroscopic and crystallographic properties.

The non-benzenoid aromatic system azulene is sufficiently nucleophilic at C1 that it can react with a protonated aldehyde to form an α-azulenyl alcohol. This in turn may be protonated and undergo loss of water to give an azulene α-carbocation. We report the isolation of such azulenyl cations as salts with non-coordinating anions.

Azulene-based fluorescent chemosensor for adenosine diphosphate.

AzuFluor® 435-DPA-Zn, an azulene fluorophore bearing two zinc(II)-dipicolylamine receptor motifs, exhibits fluorescence enhancement in the presence of adenosine diphosphate. Selectivity for ADP over ATP, AMP and PPi results from appropriate positioning of the receptor motifs, since an isomeric sensor cannot discriminate between ADP and ATP.

Role of S100A8/A9 for Cytokine Secretion, Revealed in Neutrophils Derived from ER-Hoxb8 Progenitors.

S100A9, a Ca-binding protein, is tightly associated to neutrophil pro-inflammatory functions when forming a heterodimer with its S100A8 partner. Upon secretion into the extracellular environment, these proteins behave like damage-associated molecular pattern molecules, which actively participate in the amplification of the inflammation process by recruitment and activation of pro-inflammatory cells. Intracellular functions have also been attributed to the S100A8/A9 complex, notably its ability to regulate nicotinamide adenine dinucleotide phosphate (NADPH) oxidase activation.

Opioid use disorder treatment disruptions during the early COVID-19 pandemic and other emergent disasters: a scoping review addressing dual public health emergencies.

Background: During public health emergencies, people with opioid use disorder (PWOUD) may be particularly impacted. Emergent disasters such as the COVID-19 pandemic disrupt already-strained harm reduction efforts and treatment availability. This study aims to answer three research questions.

Measurement of Pharmacist-Physician Collaborative Care on Therapeutic Inertia in Patients With Type 2 Diabetes.

Background: Team-based care practice models have been shown to improve diabetes-related therapeutic inertia, yet the method and type of antidiabetic treatment intensification (TI) leading to improvements in glycemic control are not well understood.

Objective: To evaluate time to TI in a pharmacist-physician practice model (PPM) as compared with usual medical care (UMC), explore the method and type of antidiabetic TI, and evaluate achievement of hemoglobin A (A1C) goal among each cohort.

Methods: This was a retrospective cohort study conducted between January 1, 2017, and December 31, 2018.

Ocular Filariasis in Human Caused by Breinlia (Johnstonema) annulipapillata Nematode, Australia.

We report a human case of ocular filariasis, caused by a species of Breinlia nematode, from Queensland, Australia. Morphological and molecular evidence indicated that the nematode Breinlia (Johnstonema) annulipapillata, or a closely related taxon, likely transmitted from a macropodid marsupial host was involved, which might represent an accidental finding or an emerging zoonosis.

Rapid Micro-induction of Buprenorphine/Naloxone for Opioid Use Disorder in a Critically ill Intubated Patient: A Case Report.

Background: Buprenorphine/naloxone has been shown to be an effective treatment of opioid use disorder. According to the Canadian National clinical practice guideline on the management of opioid use disorders, given the superior safety profile of buprenorphine/naloxone and its potential for flexible take-home dosing in comparison to other opioid agonist medication it is strongly recommended to initiate opioid agonist treatment with buprenorphine/naloxone as the preferred first-line treatment when possible. Due to its pharmacological properties induction can be challenging, requiring the cessation of all opioids for a certain amount of time to avoid the risk of precipitated withdrawal symptoms.

Identification of emergency department patients for referral to rapid-access addiction services.

Objectives: Substance-related emergency department (ED) visits are rapidly increasing. Despite this finding, many EDs do not have access to on-site addiction services. This study characterized substance-related ED presentations and assessed the ED health care team's perceived need for an on-site rapid-access addiction clinic for direct patient referral from the ED.

Calcium signaling and regulation of neutrophil functions: Still a long way to go.

Neutrophils are the most abundant leukocytes in blood and disruption in their functions often results in an increased risk of serious infections and inflammatory autoimmune diseases. Following recent discoveries in their influence over disease progression, a resurgence of interest for neutrophil biology has taken place. The multitude of signaling pathways activated by the engagement of numerous types of receptors, with which neutrophils are endowed, reflects the functional complexity of these cells.

Rapid Induction of Buprenorphine/Naloxone for Chronic Pain Using a Microdosing Regimen: A Case Report.

Buprenorphine is an effective treatment for chronic pain and may reduce opioid-induced hyperalgesia. However, its pharmacological properties make its induction challenging, time-consuming, and can precipitate opioid withdrawal. We present the case of a 66-year-old woman with inadequately controlled postoperative pain despite escalating doses of oxycodone and methadone, who was successfully transitioned to buprenorphine/naloxone using a rapid microinduction technique without precipitating opioid withdrawal.

Pentaerythritol Derived Tetrapode Exhibiting a Nematic-Like Mesophase at Ambient Temperatures.

The nematic liquid-crystalline phase exhibits average orientational order, with no positional organisation. So-called modulated nematic phases exhibit this same orientational order with an additional spatially periodic modulation of the nematic director, the most common of which is the twist-bend nematic phase. We report a pentaerythritol derived tetrapode which exhibits a nematic-like mesophase at ambient temperature, and we denote this new mesophase 'N ' to indicate a nematic phase of unknown structure.

Secretion of the Phosphorylated Form of S100A9 from Neutrophils Is Essential for the Proinflammatory Functions of Extracellular S100A8/A9.

S100A8 and S100A9 are members of the S100 family of cytoplasmic EF-hand Ca-binding proteins and are abundantly expressed in the cytosol of neutrophils. In addition to their intracellular roles, S100A8/A9 can be secreted in the extracellular environment and are considered as alarmins able to amplify the inflammatory response. The intracellular activity of S100A8/A9 was shown to be regulated by S100A9 phosphorylation, but the importance of this phosphorylation on the extracellular activity of S100A8/A9 has not yet been extensively studied.

The proteomic response of sea squirts (genus Ciona) to acute heat stress: a global perspective on the thermal stability of proteins.

Congeners belonging to the genus Ciona have disparate distributions limited by temperature. Ciona intestinalis is more widespread with a cosmopolitan distribution ranging from tropical to sub-arctic zones, while Ciona savignyi is limited to temperate-latitudes of the northern Pacific Ocean. To compare the heat stress response between congeners, we quantified changes in protein expression using proteomics.

Dementia care planning: shared experience and collaboration.

The perceived care challenges faced by family caregivers and healthcare providers in providing dementia care and the supports they need to address these challenges are the two key areas of exploration in this descriptive study. The perceptions were explored through semi-structured interviews and a focus group. The results from this study identified that families and healthcare providers can be partners in planning dementia care provided that they communicate effectively about their experiences and approaches to care in a climate that encourages participation and cooperation.

Postoperative cilium entrapment by clear corneal incision.

A 75-year-old man had routine phacoemulsification cataract extraction with posterior chamber intraocular lens implantation in the left eye using a temporal corneal incision and inferior paracentesis. Examinations at 1 day and 1 week were unremarkable; however, at the 6-week assessment, a cilium was noted to have penetrated the external ostium of the paracentesis, with the proximal (follicle) end abutting the internal ostium of the wound. While the cilium was removed without incident, this chance finding may aid our understanding of how intraocular cilia are occasionally discovered following routine small-incision sutureless cataract surgery.

Phacoemulsification in anterior megalophthalmos.

This case outlines the phacoemulsification technique used to overcome the challenge of the hyperdeep anterior chamber, weak zonules, abnormal anterior capsule, and large capsular bag. Key steps included trypan blue staining of the anterior capsule, a large capsulorhexis, prolapse of the nucleus into the anterior chamber with phacoemulsification anterior to the capsulorhexis, and a posterior chamber-placed iris-clip intraocular lens. Successful visual rehabilitation is achievable in these anatomically challenging eyes.

Hand performance assessment of ten people with rheumatoid arthritis when using a range of specified saucepans.

Purpose: The aim of the pilot study was to provide information about the design and use of saucepan handles to enable clinicians and designers to specify and provide products that are more appropriate for use by people with Rheumatoid Arthritis (RA). The objectives were: to evaluate aspects of new handle design for saucepans in terms of their ease of use for people with RA; document hand grip strength and configuration (grip patterns); record relevant anthropometric data to aid the development of new designs and perform an assessment of lifting techniques used in conjunction with perceived optimum handle configuration.

Method/results: Observation and video footage show that subjects continued to use familiar, but damaging, ways of lifting the saucepan even after extensive joint protection training by occupational therapists.

A contrastive analysis of release patterns of biochemical markers of brain damage after coronary artery bypass grafting and valve replacement and their association with the neurobehavioral outcome after cardiac surgery.

Objective: The present study aimed at a comparative analysis of neurobiochemical markers of brain damage and the neurobehavioral outcome in patients undergoing either valve replacement (VR) or isolated coronary artery bypass surgery (CABG). In order to control for well known risk factors both samples were strictly matched according to age, sex and preoperative neuropsychological performance.

Methods: We analysed neurone-specific enolase (NSE) and protein S-100B (S-100B) concentrations in serial venous blood samples taken preoperatively and 1, 6, 20 and 30 h postoperatively in 36 patients undergoing VR (N = 18) or isolated CABG surgery (N = 18).