The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation.
View Article and Find Full Text PDFBackground: Evaluate imaging photoplethysmography (iPPG) as a novel noninvasive technique to assess flap perfusion in head and neck free flap reconstructive (FFR) surgeries.
Methods: Intraoperative iPPG was performed in 17 patients undergoing FFR surgery. Imaging consisted of a 30-s video from which perfusion maps were extracted, providing detailed information about blood flow and pulsatility in the flap microvasculature.
Although the reactivity of five-coordinate end-on superoxocopper(II) complexes, Cu(η-O), is dominated by hydrogen atom transfer, the majority of four-coordinate Cu(η-O) complexes published thus far display nucleophilic reactivity. To investigate the origin of this difference, we have developed a four-coordinate end-on superoxocopper(II) complex supported by a sterically encumbered bis(2-pyridylmethyl)amine ligand, dpb-BPA (), and compared its substrate reactivity with that of a five-coordinate end-on superoxocopper(II) complex ligated by a similarly substituted tris(2-pyridylmethyl)amine, dpb-TMPA (). Kinetic isotope effect (KIE) measurements and correlation of second-order rate constants ('s) versus oxidation potentials () for a range of phenols indicates that the complex [Cu(η-O)()] reacts with phenols via a similar hydrogen atom transfer (HAT) mechanism to [Cu(η-O)()].
View Article and Find Full Text PDFDrug-induced QT prolongation increases the risk of Torsade de Pointes (TdP). Drug-induced QT prolongation is a complex and unpredictable system due to many uncertainties. Risk factors such as electrolyte disturbances, heart failure and genetics play an important role in estimating the effect on QT prolongation.
View Article and Find Full Text PDFIn contrast to a tungsten nitrido complex endowed with a tripodal silanolate ligand framework, which was reported in the literature to be a dimeric species with a metallacyclic core, the corresponding molybdenum nitrides are monomeric entities comprising a regular terminal nitride unit, as proven by single-crystal X-ray diffraction (SC-XRD). Their electronic character is largely determined by the constraints imposed on the metal center by the podand ligand architecture. Mo nuclear magnetic resonance (NMR) and, to a lesser extent, N NMR spectroscopy allow these effects to be studied, which become particularly apparent upon comparison with the spectral data of related molybdenum nitrides comprising unrestrained silanolate, alkoxide, or amide ligands.
View Article and Find Full Text PDFJ Orthop Sports Phys Ther
May 2024
We aimed to develop a consensus-based rehabilitation guideline specifically designed to reduce apprehension following arthroscopic Bankart repair after traumatic anterior shoulder dislocation. Delphi-based consensus. A comprehensive list of interventions for potential inclusion in a postoperative rehabilitation guideline was developed.
View Article and Find Full Text PDFBackground: The Mayo Imaging Classification was developed to predict the rate of disease progression in patients with autosomal dominant polycystic kidney disease. This study aimed to validate its ability to predict kidney outcomes in a large multicenter autosomal dominant polycystic kidney disease cohort.
Methods: Included were patients with ≥1 height-adjusted total kidney volume (HtTKV) measurement and ≥3 eGFR values during ≥1-year follow-up.
Introduction: Accurate tools to inform individual prognosis in patients with autosomal dominant polycystic kidney disease (ADPKD) are lacking. Here, we report an artificial intelligence (AI)-generated method for routinely measuring total kidney volume (TKV).
Methods: An ensemble U-net algorithm was created using the nnUNet approach.
Background: Dysregulated energy metabolism is a recently discovered key feature of autosomal dominant polycystic kidney disease (ADPKD). Cystic cells depend on glucose and are poorly able to use other energy sources such as ketone bodies. Raising ketone body concentration reduced disease progression in animal models of polycystic kidney diseases.
View Article and Find Full Text PDFPeroxo complexes are key intermediates in water oxidation catalysis (WOC). Cobalt plays an important role in WOC, either as oxides CoO or as {Co(μ1,2-peroxo)Co} complexes, which are the oldest peroxo complexes known. The oxidation of {Co(μ1,2-peroxo)Co} complexes had usually been described to form {Co(μ1,2-superoxo)Co} complexes; however, recently the formation of {Co(μ1,2-peroxo)Co} species were suggested.
View Article and Find Full Text PDFInstantaneous heart rate (IHR) has been investigated for sleep applications, such as sleep apnea detection and sleep staging. To ensure the comfort of the patient during sleep, it is desirable for IHR to be measured in a contact-free fashion. In this work, we use speckle vibrometry (SV) to perform on-skin and on-textile IHR monitoring in a sleep setting.
View Article and Find Full Text PDFThe synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an -anchored tripodal tris(carbene) chelate is described, including a Co-supported singlet nitrene. Reaction of the Co precursor [(TIMMN)Co](PF) (TIMMN = -[2-(3-mesityl-idazolin-2-ylidene)-ethyl]amie) with -methoxyphenyl azide yields a Co imide [(TIMMN)Co(NAnisole)](PF) (). Treatment of with 1 equiv of [FeCp](PF) at -35 °C affords a formal Co imido complex [(TIMMN)Co(NAnisole)](PF) (), which features a bent Co-N(imido)-C(Anisole) linkage.
View Article and Find Full Text PDFLarge spin-orbit coupling (SOC) is an intrinsic property of the heavy elements that directly affects the electronic structures of the compounds. In this work, we report the synthesis and characterization of a monocoordinate bismuthinidene that features a rigid and bulky ligand. All magnetic measurements [superconducting quantum interference device (SQUID), nuclear magnetic resonance (NMR)] point to a diamagnetic compound.
View Article and Find Full Text PDFPolysomnography (PSG) remains the gold standard for sleep monitoring but is obtrusive in nature. Advances in camera sensor technology and data analysis techniques enable contactless monitoring of heart rate variability (HRV). In turn, this may allow remote assessment of sleep stages, as different HRV metrics indirectly reflect the expression of sleep stages.
View Article and Find Full Text PDFObjectives: Polycystic liver disease (PLD) is characterized by growth of hepatic cysts, causing hepatomegaly. Disease severity is determined using total liver volume (TLV), which can be measured from computed tomography (CT). The gold standard is manual segmentation which is time-consuming and requires expert knowledge of the anatomy.
View Article and Find Full Text PDFBackground: Imaging-based total kidney volume (TKV) and total liver volume (TLV) are major prognostic factors in autosomal dominant polycystic kidney disease (ADPKD) and end points for clinical trials. However, volumetry is time consuming and reader dependent in clinical practice. Our aim was to develop a fully automated method for joint kidney and liver segmentation in magnetic resonance imaging (MRI) and to evaluate its performance in a multisequence, multicenter setting.
View Article and Find Full Text PDFBiomed Opt Express
December 2022
Camera-based blood oxygen saturation (SpO) monitoring allows reliable measurements without touching the skin and is therefore very attractive when there is a risk of cross-infection, in case of fragile skin, and/or to improve the clinical workflow. Despite promising results, productization of the technology is hampered by the unavailability of adequate hardware, especially a camera, which can capture the optimal wavelengths for SpO measurements in the red near-infrared region. A regular color (RGB) camera is attractive because of its availability, but also poses several risks and challenges which affect the accuracy of the measurement.
View Article and Find Full Text PDFIntroduction: Anastomotic leakage after gastrointestinal surgery has a high impact on patient's quality of life and its origin is associated with inadequate perfusion. Imaging photoplethysmography (iPPG) is a noninvasive imaging technique that measures blood-volume changes in the microvascular tissue bed and detects changes in tissue perfusion.
Materials And Methods: Intraoperative iPPG imaging was performed in 29 patients undergoing an open segment resection of the small intestine or colon.
Herein, the first stable anions K[SIPr ] (4 a-K) and K[IPr ] (4 b-K) (SIPr =BpC{N(Dipp)CH } , IPr =BpC{N(Dipp)CH} ; Bp=4-PhC H ; Dipp=2,6-iPr C H ) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids.
View Article and Find Full Text PDFAnnu Int Conf IEEE Eng Med Biol Soc
July 2022
Monitoring of heart rate in patients in the general ward is necessary to assess the clinical situation of the patient. Currently, this is done via spot-checks on pulse rate manually or on heart rate using Electrocardiogram (ECG) by nurses. More frequent measurements would allow early detection of adverse cardiac events.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2022
Reaction of the Co complex [(TIMMN )Co ](PF ) (1) (TIMMN =tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with mesityl azide yields the Co imide [(TIMMN )Co (NMes)](PF ) (2). Oxidation of 2 with [FeCp ](PF ) provides access to a rare Co imidyl [(TIMMN )Co(NMes)](PF ) (3). Single-crystal X-ray diffractometry and EPR spectroscopy confirm the molecular structure of 3 and its S= ground state.
View Article and Find Full Text PDFSurgical excision is the golden standard for treatment of intestinal tumors. In this surgical procedure, inadequate perfusion of the anastomosis can lead to postoperative complications, such as anastomotic leakages. Imaging photoplethysmography (iPPG) can potentially provide objective and real-time feedback of the perfusion status of tissues.
View Article and Find Full Text PDFBackground And Objectives: The vasopressin V2 receptor antagonist tolvaptan is the only drug that has been proven to be nephroprotective in autosomal dominant polycystic kidney disease (ADPKD). Tolvaptan also causes polyuria, limiting tolerability. We hypothesized that cotreatment with hydrochlorothiazide or metformin may ameliorate this side effect.
View Article and Find Full Text PDF