Amine-Terminated Phenanthroline Diimides as Aqueous Masking Agents for Am(III)/Eu(III) Separation: An Alternative Ligand Design Strategy for Water-Soluble Lanthanide/Actinide Chelating Ligands.

Selective actinide coordination (from lanthanides) is critical for both nuclear waste management and sustainable development of nuclear power. Hydrophilic ligands used as masking agents to withhold actinides in the aqueous phase are currently highly pursued, while synthetic accessibility, water solubility, acid resistance, and extraction capability are the remaining problems. Most reported hydrophilic ligands are only effective at low acidity. We recently proved that the phenanthroline diimide skeleton was an efficient building block for the construction of highly efficient acid-resistant hydrophilic lanthanide/actinide separation agents, while the limited water solubility hindered the loading capability of the ligand. Herein, amine was introduced as the terminal solubilizing group onto the phenanthroline diimide backbone, which after protonation in acid showed high water solubility. The positively charged terminal amines enhanced the ligand water solubility to a large extent, which, on the other side, was believed to be detrimental for the coordination and complexation of the metal cations. We showed that by delicately adjusting the alkyl chain spacing, this intuitive disadvantage could be relieved and superior extraction performances could be achieved. This work holds significance for both hydrophilic lanthanide/actinide separation ligand design and, concurrently, offers insights into the development of water-soluble lanthanide/actinide complexes for biomedical and bioimaging applications.

Achieving Exceptional Thermal and Hydrolytic Resistance in Chemically Circular Polyesters via In-Chain 1,3-Cyclobutane Rings.

Polyesters, a highly promising class of circular polymers for achieving a closed-loop sustainable plastic economy, inherently exhibit material stability defects, especially in thermal and hydrolytic instability. Here, we introduce a class of polyesters, P(4R-BL) (R=Ph, Bu), featuring conformationally rigid 1,3-cyclobutane rings in the backbone. These polyesters not only exhibit superior thermostability (Td,5%=376-380 °C) but also demonstrate exceptional hydrolytic resistance with good integrity even after 1 year in basic and acidic aqueous solutions, distinguishing themselves from typical counterparts. Tailoring the flexibility of the side group R enables the controlled thermal and mechanical performance of P(4Ph-BL) and P(4Bu-BL) to rival durable syndiotactic polystyrene (SPS) and low-density polyethylene (LDPE), respectively. Significantly, despite their high stability, both polyesters can be effectively depolymerized into pristine monomers, establishing a circular life cycle.

Tandem H/D Exchange-SET Reductive Deuteration Strategy for the Synthesis of α,ß-Deuterated Amines Using D2O.

α,ß-Deuterated amines are crucial for the development of deuterated drugs. We intend to introduce the novel tandem H/D exchange-single electron transfer (SET) reductive deuteration strategy with high pot- and reagent-economy by the synthesis of α,ß-deuterated amine using nitrile as the precursor. The H/D exchange of the -CH2CN group was achieved by D2O/Et3N, which were also the required reagents in the tandem SmI2-mediated SET reductive deuteration of the α-deuterated nitrile. The potential application of this method was further showcased by the synthesis of bevantolol-d4.

Reductive Deuteration of Nitriles Using D2O as a Deuterium Source.

The first single electron transfer reductive deuteration of nitriles using D2O as a deuterium source has been developed for the synthesis of valuable α,α-dideuterio amines. A mild reductant (SmI2) was employed as the electron donor with Et3N as the additive. This reaction is amenable to both aromatic and aliphatic nitriles and features high deuterium incorporation, excellent regioselectivity, and good functional group tolerance. The synthetic utility of this protocol was demonstrated by the synthesis of a series of important deuterium-labeled building blocks for medicinal chemistry and agrochemistry applications.

Modified ventriculoperitoneal shunt applied to temporary external ventricular drainage.

External ventricular drainage (EVD) is a common procedure in neurosurgical practice. Presently, the three methods used most often include direct EVD (dEVD), long-tunneled external ventricular drains (LTEVDs), and EVD via the Ommaya reservoir (EVDvOR). But they possess drawbacks such as limited duration of retention, vulnerability to iatrogenic secondary infections, and challenges in regulating drainage flow. This study aimed to explore the use of a modified ventriculoperitoneal shunt (mVPS)-the abdominal end of the VPS device was placed externally-as a means of temporary EVD to address the aforementioned limitations. This retrospective cohort study, included 120 cases requiring EVD. dEVD was performed for 31 cases, EVDvOR for 54 cases (including 8 cases with previously performed dEVD), and mVPS for 35 cases (including 6 cases with previously performed EVDvOR). The one-time success rate (no need for further other EVD intervention) for dEVD, EVDvOR, and mVPS were 70.97%, 88.89%, and 91.42%, dEVD vs EVDvOR (P < 0.05), dEVD vs mVPS (P < 0.05), EVDvOR vs mVPS (P > 0.05). Puncture needle displacement or detachment was observed in nearly all cases of EVDvOR, while no such complications have been observed with mVPS. Apart from this complication, the incidence of postoperative complications was 35.48%, 14.81%, and 8.5%, dEVD vs EVDvOR (P < 0.05), dEVD vs mVPS (P < 0.05), EVDvOR vs mVPS (P > 0.05). Mean postoperative retention for EVD was 14.68 ± 9.50 days, 25.96 ± 15.14 days, and 82.43 ± 64.45 days, respectively (P < 0.001). In conclusion, mVPS significantly extends the duration of EVD, which is particularly beneficial for patients requiring long-term EVD.

Diagnosis and Management of Pediatric Papillary Craniopharyngiomas.

OBJECTIVE: Papillary craniopharyngioma (PCP) was previously believed to occur only in adults. Sporadic pediatric PCP (PPCP) confirmed by detection of BRAF V600E mutation has been reported since 2018, but is often misdiagnosed before being diagnosed definitively. We aimed to evaluate PPCP characteristics and propose diagnostic criteria for prompt diagnosis, seeking to reduce patient morbidity and mortality and reduce costs linked to misdiagnosis. METHODS: This study included 5 patients with PPCPs whose data were retrieved retrospectively from among 1032 patients with craniopharyngiomas admitted to Sanbo Brain Hospital Management Group from March 2017 to May 2021. Patients' demographics, clinical presentation, tumor imaging characteristics, histopathologic results, surgical approaches, and postoperative outcomes were analyzed. RESULTS: PPCP was misdiagnosed intraoperatively as sellar abscess (n = 4) or Rathke cleft cyst (n = 1). Preoperative magnetic resonance imaging showed that all tumors were under the saddle diaphragm, and the cyst wall was enhanced (n = 5). Computed tomography scans showed scattered high-density signs (n = 4). No recurrence was noted after complete resection. Postoperative hypothalamic dysfunction was mild. BRAF V600E mutation was confirmed in all cases by sequencing and immunohistochemistry. Immunohistochemistry showed granulation and inflammation and MPO, CD3, CD20, CD38, CD68, and CD163 were positively expressed. CONCLUSIONS: Misdiagnosis of PPCP is responsible for failed surgical treatment. We propose that prompt diagnosis of PPCP can be achieved if preoperative magnetic resonance images show the tumor under saddle diaphragm with tumor wall enhancement and computed tomography scans show high-density signs scattered in the tumor, which leads to safe, effective tumor resection. Our proposed diagnosis and treatment strategy for PPCP reduces morbidity and mortality.