Site-Specific Metal Chelation Facilitates the Unveiling of Hidden Coordination Sites in an Fe II/Fe III -Seamed Pyrogallol[4]arene Nanocapsule

Under suitable conditions, C-alkylpyrogallol­[4]­arenes (PgCs) arrange into spherical metal–organic nanocapsules (MONCs) upon coordination to appropriate metal ions. Herein we present the synthesis and structural characterization of a novel FeII/FeIII-seamed MONC, as well as studies related to its electrochemical and magnetic behaviors. Unlike other MONCs that are assembled through 24 metal ions, this nanocapsule comprises 32 Fe ions, uncovering 8 additional coordination sites situated between the constituent PgC subunits. The FeII ions are likely formed by the reducing ability of DMF used in the synthesis, representing a novel synthetic route toward polynuclear mixed-valence MONCs

Impact of opioid-free analgesia on pain severity and patient satisfaction after discharge from surgery: multispecialty, prospective cohort study in 25 countries

Background: Balancing opioid stewardship and the need for adequate analgesia following discharge after surgery is challenging. This study aimed to compare the outcomes for patients discharged with opioid versus opioid-free analgesia after common surgical procedures.Methods: This international, multicentre, prospective cohort study collected data from patients undergoing common acute and elective general surgical, urological, gynaecological, and orthopaedic procedures. The primary outcomes were patient-reported time in severe pain measured on a numerical analogue scale from 0 to 100% and patient-reported satisfaction with pain relief during the first week following discharge. Data were collected by in-hospital chart review and patient telephone interview 1 week after discharge.Results: The study recruited 4273 patients from 144 centres in 25 countries; 1311 patients (30.7%) were prescribed opioid analgesia at discharge. Patients reported being in severe pain for 10 (i.q.r. 1-30)% of the first week after discharge and rated satisfaction with analgesia as 90 (i.q.r. 80-100) of 100. After adjustment for confounders, opioid analgesia on discharge was independently associated with increased pain severity (risk ratio 1.52, 95% c.i. 1.31 to 1.76; P < 0.001) and re-presentation to healthcare providers owing to side-effects of medication (OR 2.38, 95% c.i. 1.36 to 4.17; P = 0.004), but not with satisfaction with analgesia (beta coefficient 0.92, 95% c.i. -1.52 to 3.36; P = 0.468) compared with opioid-free analgesia. Although opioid prescribing varied greatly between high-income and low- and middle-income countries, patient-reported outcomes did not.Conclusion: Opioid analgesia prescription on surgical discharge is associated with a higher risk of re-presentation owing to side-effects of medication and increased patient-reported pain, but not with changes in patient-reported satisfaction. Opioid-free discharge analgesia should be adopted routinely

Zinc(II)-Directed Self-Assembly of Metal–Organic Nanocapsules

A metal–organic nanocapsule consisting of 24 Zn²⁺ ions and six pyrogallol[4]­arene units has been synthesized and structurally characterized. All the Zn²⁺ ions seaming the nanocapsule are disordered over two positions forming concave distortions on the framework

Investigating Reaction Conditions To Control the Self-Assembly of Cobalt-Seamed Nanocapsules

The synthesis and X-ray crystallographic structure of the first cobalt-seamed hexameric nanocapsule, [Co₂₄(<i>C</i>-pentylpyrogallol­[4]­arene)₆], is presented. The overall metal–ligand arrangement of this novel capsule is similar to that of previously reported copper- and nickel-seamed hexameric nanocapsules. However, the title nanocapsule encloses a larger void space than those found in previous hexameric nanocapsules

Introducing Defects into Metal-Seamed Nanocapsules Using Mixed Macrocycles

The synthesis and single-crystal X-ray diffraction structure of a dimeric zinc-seamed nanocapsule using a mixed pyrogallol/resorcinol[4]­arene are presented. The use of “mixed” macrocycles results in an incomplete seam of coordination bonds around the nanocapsule’s typically octa-metalated belt. The self-assembly of the nanocapsule occurs such that the single resorcinol moiety of each macrocycle aligns transversely. This yields a hepta-metalated capsule where the defect occurs in such a way as to provide minimal disruption to the overall structure of the nanocapsule

Introducing Defects into Metal-Seamed Nanocapsules Using Mixed Macrocycles

The synthesis and single-crystal X-ray diffraction structure of a dimeric zinc-seamed nanocapsule using a mixed pyrogallol/resorcinol[4]­arene are presented. The use of “mixed” macrocycles results in an incomplete seam of coordination bonds around the nanocapsule’s typically octa-metalated belt. The self-assembly of the nanocapsule occurs such that the single resorcinol moiety of each macrocycle aligns transversely. This yields a hepta-metalated capsule where the defect occurs in such a way as to provide minimal disruption to the overall structure of the nanocapsule