The ability to continually monitor target ion species in real-time is a highly sought-after endeavour in the field of host-guest chemistry, given its direct pertinence to medical and environmental applications. Developing methodologies which support sensitive and continuous ion sensing in aqueous media, however, remains a challenge. Herein, we present a versatile and facile, proof-of-concept electrochemical sensing methodology based on non-faradaic capacitance, which can be operated continuously with high temporal resolution (≈1.
View Article and Find Full Text PDFAn ion-responsive MRI contrast agent based on a POPC liposomal scaffold is generated that displays a large amplitude relaxivity switch. Entrapment of MR active Gd-DOTA within cholesterol-doped, , membrane rigidified, liposomes dampens the MR response through diminished water exchange across the lipid bilayer. Relaxivity is re-established by integration of ion carriers in the liposome membrane to mediate solvated ion flux.
View Article and Find Full Text PDFCirculating tumour cells (CTCs) are cancer cells shed from a primary tumour which intravasate into the blood stream and have the potential to extravasate into distant tissues, seeding metastatic lesions. As such, they can offer important insight into cancer progression with their presence generally associated with a poor prognosis. The detection and enumeration of CTCs is, therefore, critical to guiding clinical decisions during treatment and providing information on disease state.
View Article and Find Full Text PDFAnion recognition is pertinent to a range of environmental, medicinal and industrial applications. Recent progress in the field has relied on advances in synthetic host design to afford a broad range of potent recognition motifs and novel supramolecular structures capable of effective binding both in solution and at derived molecular films. However, performance in aqueous media remains a critical challenge.
View Article and Find Full Text PDFAs a tumor-suppressing protein, p53 plays a crucial role in preventing cancer development. Its utility as an early cancer detection tool is significant, potentially enabling clinicians to forestall disease advancement and improve patient prognosis. In response to the pathological overexpression of this antigen in tumors, the prevalence of anti-p53 antibodies increases in serum, in a manner quantitatively indicative of cancer progression.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2024
Anion sensing via either optical or electrochemical readouts has separately received enormous attention, however, a judicious combination of the advantages of both modalities remains unexplored. Toward this goal, we herein disclose a series of novel, redox-active, fluorescent, halogen bonding (XB) and hydrogen bonding (HB) BODIPY-based anion sensors, wherein the introduction of a ferrocene motif induces remarkable changes in the fluorescence response. Extensive fluorescence anion titration, lifetime and electrochemical studies reveal anion binding-induced emission modulation through intramolecular photoinduced electron transfer (PET), the magnitude of which is dependent on the nature of both the XB/HB donor and anion.
View Article and Find Full Text PDFImportance: Nonmotor symptoms of Parkinson disease (PD) often predate the movement disorder by decades. Currently, there is no blood biomarker to define this prodromal phase.
Objective: To investigate whether α-synuclein in neuronally derived serum-extracellular vesicles identifies individuals at risk of developing PD and related dementia.
We describe a new synthetic methodology for the preparation of high quality, emission tuneable InP-based quantum dots (QDs) using a solid, air- and moisture-tolerant primary phosphine as a group-V precursor. This presents a significantly simpler synthetic pathway compared to the state-of-the-art precursors currently employed in phosphide quantum dot synthesis which are volatile, dangerous and air-sensitive, P(Si(CH)).
View Article and Find Full Text PDFBackground: The purpose of this study was to retrospectively examine the relationship between preoperative and postoperative alignment in robotic unicompartmental knee arthroplasty (UKA) and postoperative patient-reported outcome measures.
Methods: A retrospective review of 374 patients who underwent robotic-assisted UKA was conducted. Patient demographics, history, and preoperative and postoperative Knee Injury and Osteoarthritis Outcome Score for Joint Replacement (KOOS-JR) scores were obtained via chart review.
The analysis of cargo proteins in exosome subpopulations has considerable value in diagnostics but a translatable impact has been limited by lengthy or complex exosome extraction protocols. We describe herein a scalable, fast, and low-cost exosome extraction using an alternating (AC) magnetic field to support the dynamic mixing of antibody-coated magnetic beads (MBs) with serum samples within 3D-printed microfluidic chips. Zwitterionic polymer-coated MBs are, specifically, magnetically agitated and support ultraclean exosome capture efficiencies >70% from <50 μL of neat serum in 30 min.
View Article and Find Full Text PDFBackground: Intravenous dexamethasone has been shown to reduce pain in total joint arthroplasty. This double-blind, randomized, placebo-controlled trial investigated the postoperative effects and safety of oral dexamethasone as a potential augment to multimodal pain management in outpatient knee arthroplasty.
Methods: The authors prospectively randomized 109 consecutive patients undergoing primary total knee arthroplasty.
We introduce a facile assessment of binding kinetics at bioreceptive redox-active interfaces as a means of quantifying target proteins. This is achieved by monitoring the redox capacitance () of a receptor-modified conductive polymer interface under continuous flow. Exemplified with the quantification of C-reactive protein (CRP), capacitance analyses resolve both the association and dissociation regimes in real-time.
View Article and Find Full Text PDFMimicking Nature's polymeric protein architectures by designing hosts with binding cavities screened from bulk solvent is a promising approach to achieving anion recognition in competitive media. Accomplishing this, however, can be synthetically demanding. Herein we present a synthetically tractable approach, by directly incorporating potent supramolecular anion-receptive motifs into a polymeric scaffold, tuneable through a judicious selection of the co-monomer.
View Article and Find Full Text PDFChem Commun (Camb)
February 2023
Paramagnetically-doped polymer micelles, containing an ionizable poly(acrylic acid) (PAA) block, support high-contrast MR imaging at clinically relevant field strengths in a manner that is strongly pH responsive. A reversible switch in polymer strand charge specifically has a direct impact on local rigidity, and rotational correlation time characteristics, of the integrated Gd-chelate, driving a ∼50% amplitude switch in positive contrast.
View Article and Find Full Text PDFWe introduce a novel electrochemical protein quantitation based on the shotgun biotin tagging of proteins prior to their interfacial immunocapture and polymeric enzyme tagging. The highly amplified faradaic signals generated from a novel ferrocene-tyramine adduct enable fg mL (attomolar) levels of detection and span cross a 5 orders of magnitude dynamic range. This work supports ultrasensitive protein marker detection in a single antibody immunoassay format.
View Article and Find Full Text PDFThe development of diagnostic devices relies heavily on the immobilization of biomolecules on supportive substrates, that is the generation of interfaces that can thereafter produce a quantifiable signal upon exposure to a specific target. The ability of a biosensor to selectively recruit analytes is highly dependent on the quality of this receptive biolayer and its functionality. Key performance metrics are selectivity and sensitivity and both are highly dependent on the interfacial structural and physical properties, though often these are not well resolved; in many cases analyses are performed, for example with little knowledge of receptor surface coverage, orientation and/or distribution.
View Article and Find Full Text PDFBackground: It is not well understood how patient reported outcome measures (PROMs) change from initial presentation to day-of-surgery (DOS). This study sought to quantify preoperative PROM changes for hip and knee arthroplasty patients.
Methods: A retrospective review was performed on primary total hip, total knee, and partial knee arthroplasty patients from October 2020 through January 2021.
The purpose of this article is to describe the use of ultrasound for the diagnosis and treatment of painful joint arthroplasty. Ultrasound plays a crucial role in the diagnosis of the painful joint arthroplasty, especially given its unique dynamic capabilities, convenience, and high resolution. Ultrasound guidance is also instrumental for procedures in both diagnosing and in select cases, treating the painful joint arthroplasty.
View Article and Find Full Text PDFInspired by the success of its related sigma-hole congener halogen bonding (XB), chalcogen bonding (ChB) is emerging as a powerful noncovalent interaction with a plethora of applications in supramolecular chemistry and beyond. Despite its increasing importance, the judicious modulation of ChB donor strength remains a formidable challenge. Herein, we present, for the first time, the reversible and large-scale modulation of ChB potency by electrochemical redox control.
View Article and Find Full Text PDFBackground: Robotic-assisted total hip arthroplasty (R-THA) affords precision yet uncertain clinical benefits. This study compares dislocation rates and related revisions between R-THA and manual total hip arthroplasty (M-THA). Secondarily we evaluated cup position, patient-reported outcome measures (PROMs), and postoperative complications.
View Article and Find Full Text PDFThe progressive emergence of protein biomarkers promises a revolution in the healthcare industry and a shift of focus from disease management to much earlier intervention. Here, we introduce a facile shotgun tagging of ensemble proteins in clinically relevant media prior to specific target capture at antibody-modified electrodes. This facilitates a convenient voltammetric quantification of markers down to sub-pg/mL levels and across several orders of concentration.
View Article and Find Full Text PDFContrast agents retaining high relaxivities at ultrahigh magnetic fields underpin an enhanced image sensitivity within derived MRI scans. By varying the Dy loading density inside a mesoporous silica architecture the dominant Curie effect can be effectively tuned so as to optimise contrast at magnetic fields as high as 11.7 T.
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