Synergizing Steric Hindrance and Stacking Interactions To Facilitate the Controlled Assembly of Multiple 41 Metalla-Knots and Pseudo-Solomon Links.

In this work, a noncoplanar terphenyl served as a building block to synthesize a novel 3,3'-substituted bipyridyl ligand (L1) which further reacted with binuclear half-sandwich units A/B, giving rise to two aesthetic 41 metalla-knots in high yields via a coordination-driven self-assembly strategy. Furthermore, given the inherent compactness of the 41 metalla-knots, it creates favorable conditions for the emergence of steric repulsion. We focused on progressively introducing nitrogen atoms featuring a lone pair of electrons (LPEs) into ligand L1 to manipulate the balance of H⋅⋅⋅H/LPEs⋅⋅⋅LPEs steric repulsion during the assembly process, ultimately achieving controlled assembly from 41 metalla-knots to the pseudo-Solomon link and then to molecular tweezer-like assembly facilitated by stacking interactions. All the assemblies were well characterized by solution-state NMR techniques, ESI-TOF/MS, and single-crystal X-ray diffraction. The evolutionary process of the topological architectures is equivalent to visualizing the synergistic effect of steric hindrance and stacking interactions on structural assembly, providing a new avenue for achieving the controlled synthesis of different topologies.

The codriven assembly of molecular metalla-links ([Formula: see text], [Formula: see text]) and metalla-knots ([Formula: see text], [Formula: see text]) via coordination and noncovalent interactions.

Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for their synthesis. Herein, we presented a synergistic assembly strategy based on coordination and noncovalent interactions (π-π stacking and CH⋯π interactions) to selectively synthesize molecular closed three-link chains ([Formula: see text] links), highly entangled figure-eight knots ([Formula: see text] knots), trefoil knot ([Formula: see text] knot), and Borromean ring ([Formula: see text] link). [Formula: see text] links can be created by the strategic assembly of nonlinear multicurved ligands incorporating a furan or phenyl group with the long binuclear half-sandwich organometallic Cp*RhIII (Cp* = η5-pentamethylcyclopentadienyl) clip. However, utilizing much shorter binuclear Cp*RhIII units for union with the 2,6-naphthyl-containing ligand led to a [Formula: see text] knot because of the increased π-π stacking interactions between four consecutive stacked layers and CH⋯π interactions. Weakening such π-π stacking interactions resulted in a [Formula: see text] knot. The universality of this synergistic assembly strategy for building [Formula: see text] knots was verified by utilizing a 1,5-naphthyl-containing ligand. Quantitative conversion between the [Formula: see text] knot and the simple macrocycle species was accomplished by adjusting the concentrations monitored by NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing the stiff π-conjugated area of the binuclear unit afforded molecular Borromean ring, and this topology is a topological isomer of the [Formula: see text] link. These artificial metalla-links and metalla-knots were confirmed by single-crystal X-ray diffraction, NMR and ESI-MS. The results offer a potent strategy for building higher-order MIMs and emphasize the critical role that noncovalent interactions play in creating sophisticated topologies.

The Topological Transformation of Trefoil Knots to Solomon Links via Diels-Alder Click Reaction.

The quest for more efficient, user-friendly, and less wasteful topological transformations remains a significant challenge in the realm of postassembly modifications. In this article, high yields of two molecular trefoil knots (Rh-1, Ir-1) were obtained using ligand 3,6-bis(3-(pyridin-4-yl)phenyl)-1,2,4,5-tetrazine (L1) with reactive tetrazine units and binuclear half-sandwich organometallic units [Cp*2M2(µ-TPPHZ)(OTf)2](OTf)2 (Rh-B, M = RhIII; Ir-B, M = IrIII). 2,5-Norbornadiene was used as an inducer of the Diels-Alder click reaction to modulate rapidly and efficiently the transformation of Trefoil knots to Solomon links. However, the key to achieving this topological structural change is the subtle increase in site steric of the pyridazine fragments (L2), which allows the molecular structures to spread and bend in three-dimensional space, as confirmed by single-crystal X-ray diffraction, ESI-TOF/MS, elementary analysis and detailed solution-state NMR techniques.

Primary pulmonary meningioma and minute pulmonary meningothelial-like nodules: Rare pulmonary nodular lesions requiring more awareness in clinical practice.

In this editorial, we comment on an article by Ruan et al published in a recent issue of the World Journal of Clinical Case. Pulmonary meningothelial proliferative lesions, including primary pulmonary meningiomas, minute pulmonary meningothelial-like nodules, and metastatic pulmonary meningiomas are rare pulmonary lesions. These lesions are difficult to differentiate from lung cancers based on clinical and imaging manifestations. Herein, we briefly introduce the clinical, imaging, and pathological characteristics of these lesions and discuss their pathogenesis to strengthen the current understanding of pulmonary meningothelial proliferative lesions in clinical diagnosis and therapy.

Efficient and Selective Construction of 41 2 Metalla-links Using Weak C-H⋠⋠⋠Halogen Interactions.

Through a coordination-driven self-assembly method, four 4 1 2 ${4_1^2 }$ metalla-links and one tetranuclear monocycle were constructed with high selectivity and yield by adjusting the substituent species of the building blocks, as evidenced using X-ray crystallographic analysis, electrospray ionization-time-of-flight/mass spectrometry (ESI-TOF/MS), elemental analysis and detailed solution-state nuclear magnetic resonance (NMR) spectroscopy. Based on X-ray crystallographic analysis and independent gradient model analysis, a significant factor leading to the formation of 4 1 2 ${4_1^2 }$ metalla-links was the introduction of F, Cl, Br and I atoms, which generated additional weak C-H⋅⋅⋅X (X=F, Cl, Br and I) interactions. Furthermore, the dynamic conversion of 4 1 2 ${4_1^2 }$ metalla-links to monocyclic rings in methanol solution was systematically investigated using quantitative 1H NMR techniques.

Selective B(3)-H Activation Affording Multinuclear Ir(III) Complexes with (o-Carboranyl)dithioester Ligands.

A method was developed to link two or three o-carborane moieties to form a series of carboranyl dithioester bridging ligands via in situ substitution of haloalkanes by tetraphenylphosphonium carboranyldithiocarboxylates. Based on these ligands, direct B-H activation without the assistance of Ag(I) and alkali was successfully achieved with half-sandwich Ir(III) substrate [Cp*IrCl2]2 to yield corresponding bimetallic or trimetallic complexes. Single crystal structure analyses of the B-H activated complexes and corresponding SnCl2-inserted derivatives confirm the selective B(3)-H activation in these complexes.

Efficacy comparison between acupuncture and other modalities in the treatment of rotator cuff diseases: meta-analysis of randomized controlled trials.

OBJECTIVE: This study aimed to analyze the efficacy of acupuncture alone or combined with physical therapy compared to other treatment interventions for relieving pain and improving function in rotator cuff diseases. METHODS: Our study followed the Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. After PROSPERO (CRD42023396740) registration, all randomized controlled trials (RCTs) published from the inception of the databases to October 10, 2023, evaluating the efficacy of acupuncture either alone or in combination with physical therapy for treating rotator cuff diseases, were extracted from seven databases, including PubMed, Embase, the Web of Science, the Cochrane Library, the China National Knowledge Infrastructure (CNKI), the VIP Database for Chinese Technical Periodicals (VIP), and the Wanfang Date. Two independent researchers assessed the quality of the included studies and extracted relevant data. Furthermore, a meta-analysis was conducted using Stata 14 software. RESULTS: We included 13 RCTs - 12 published in English and 1 in Chinese - that enrolled 1,371 patients. The meta-analysis results demonstrated that acupuncture alone or in combination with physical therapy was superior to other interventions for short-term shoulder joint function improvement (standardized mean difference [SMD] = -0.82, 95% confidence interval [95% CI]: -1.28 to -0.35, P = 0.001), medium-term shoulder joint function improvement (SMD = -1.00, 95% CI: -1.62 to -0.38, P = 0.002), short-term pain relief (weighted mean difference [WMD] = -1.37, 95% CI: -2.39 to -0.38, P = 0.006), medium-term pain relief (WMD = -1.66, 95% CI: -2.70 to -0.63, P = 0.002), and post-treatment shoulder joint abduction improvements (SMD = 0.68, 95% CI: 0.20 to 1.16, P = 0.005), external rotation (SMD = 0.62, 95% CI: 0.13 to 1.11, P = 0.012), and forward flexion (SMD = 0.71, 95% CI: 0.44 to 0.97, P < 0.001), with significant differences (P < 0.05). CONCLUSION: Based on the current clinical data, meta-analysis showed that acupuncture alone or combined with physical therapy is efficacious for short- and medium-term (< 3 months) pain relief and functional improvements. However, compared to other interventions, the efficacy of the long-term (3 to 12 months) period did not significantly differ. After treatment, these modalities displayed advantages such as improved shoulder joint abduction, external rotation, and forward flexion movements. However, no significant difference was noted in internal rotation movement. Thus, future studies might further investigate whether different acupuncture methods affect the efficacy of treating rotator cuff diseases and improving long-term outcome.

Primary adenomatoid tumor of the adrenal gland: A case report and literature review.

RATIONALE: Adenomatoid tumors are rare benign tumors, mainly involving the reproductive tract, such as the epididymis in men and the uterus and fallopian tubes in women. However, a few cases can occur outside the reproductive tract. Herein, we report a rare case of a primary adenomatoid tumor of the adrenal gland. PATIENT CONCERNS: A 50-year-old man underwent ultrasound examination and was found to have a right adrenal mass without elevated blood pressure, weakness after fatigue, frequent nocturnal urination urgency, pain, or a history of hematuria. The patient's general health was normal. Computed tomography revealed a polycystic mixed-density lesion in the right adrenal region, approximately 7.3 × 4.5 cm in size. DIAGNOSES: Based on the clinical information, morphological features, and immunohistochemistry results, a pathological diagnosis of primary adenomatoid tumor of the adrenal gland was made. INTERVENTION: Excision of the right adrenal gland and tumor through the 11 ribs. OUTCOMES: The patient's postoperative course was uneventful. LESSONS: Preventing misdiagnosis adenomatoid tumors with other types of adrenal gland tumors or metastatic tumors is imperative. Morphological and immunohistochemical features can help diagnose primary adenomatoid tumors of the adrenal gland.