Recent strategies for constructing hierarchical multicomponent nanoparticles/metal-organic framework hybrids and their applications.

Hybrid nanoparticles with unique tailored morphologies and compositions can be utilized for numerous applications owing to their combination of inherent properties as well as the structural and supportive functions of each component. Controlled encapsulation of nanoparticles within nanospaces (NPNSs) of metal-organic frameworks (MOFs) (denoted as NPNS@MOF) can generate a large number of hybrid nanomaterials, facilitating superior activity in targeted applications. In this review, recent strategies for the fabrication of NPNS@MOFs with a hierarchical architecture, tailorability, unique intrinsic properties, and superior catalytic performance are summarized. In addition, the latest and most important examples in this sector are emphasized since they are more conducive to the practical applicability of NPNS@MOF nanohybrids.

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks.

Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M6 and P6 discrete racemic cage molecules (M6 - cage with six M-TSHs; P6 - cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methylisophthalate bridging ligands was synthesized for host-guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.

Fabrication of hollow fibrous nanosilica with large pore channels.

The fabrication of hollow mesoporous nanosilica with well-defined structural features for optimizing the integration of functional components is a challenge. Herein, we report a facile preparation of hollow fibrous nanosilica (HFNS) with high specific surface area (666 m2 g-1), fiber-like mesoporous architectures in the inner and outer shells, and large pore channels (16.22 nm) via selective self-etching of dendritic fibrous nanosilica in an aqueous medium. The specific surface area and pore diameter increased significantly after the formation of a cavity in the center, resulting in HFNS. The HFNS can serve as a robust support for the controllable growth of gold nanoparticles with maximum catalytic performance for 4-nitrophenol reduction.

Controllable Nitric Oxide Storage and Release in Cu-BTC: Crystallographic Insights and Bioactivity.

Crystalline metal-organic frameworks (MOFs) are extensively used in areas such as gas storage and small-molecule drug delivery. Although Cu-BTC (1, MOF-199, BTC: benzene-1,3,5-tricarboxylate) has versatile applications, its NO storage and release characteristics are not amenable to therapeutic usage. In this work, micro-sized Cu-BTC was prepared solvothermally and then processed by ball-milling to prepare nano-sized Cu-BTC (2). The NO storage and release properties of the micro- and nano-sized Cu-BTC MOFs were morphology dependent. Control of the hydration degree and morphology of the NO delivery vehicle improved the NO release characteristics significantly. In particular, the nano-sized NO-loaded Cu-BTC (NO⊂nano-Cu-BTC, 4) released NO at 1.81 µmol·mg-1 in 1.2 h in PBS, which meets the requirements for clinical usage. The solid-state structural formula of NO⊂Cu-BTC was successfully determined to be [CuC6H2O5]·(NO)0.167 through single-crystal X-ray diffraction, suggesting no structural changes in Cu-BTC upon the intercalation of 0.167 equivalents of NO within the pores of Cu-BTC after NO loading. The structure of Cu-BTC was also stably maintained after NO release. NO⊂Cu-BTC exhibited significant antibacterial activity against six bacterial strains, including Gram-negative and positive bacteria. NO⊂Cu-BTC could be utilized as a hybrid NO donor to explore the synergistic effects of the known antibacterial properties of Cu-BTC.

Complete resection for a giant recurrent biliary cystadenoma: A surgical case report and review of literature.

Background: Biliary cystadenoma is a rare cystic neoplasm of the liver. The clinical signs and symptoms are nonspecific, and treatment strategy is variable. Case presentation: In this study, we presented a case of a 32-year-old female with multilocular biliary cystadenoma. The patient underwent partial removal of the hepatic cyst two times in two different hospitals for two years and that the histopathological results were biliary cystic adenoma but was successfully treated by radical resection after the second recurrence. The patient underwent a J-shaped laparotomy. The giant cystic mass measuring 20 cm × 15 cm was below the position of the right anterior segment. This lesion pushed the liver parenchyma to both sides and compressed the hepatic hilum, causing dilatation of the intrahepatic bile ducts. The patient underwent complete resection of cystic mass. During the dissection, a 0.5mm-diameter fistula of left hepatic duct with the cyst was found. It was sutured using absorbable polydioxanone (PDS 6.0) and the cystic duct tube (C tube) (6 Fr) was inserted via the cystic duct into the left hepatic duct due to drain the bile fluid. Discussion: A biliary cystadenoma (BCA) primary origin is occasionally rare. Although imaging modalities such as ultrasound, computed tomography and magnetic resonance imaging could be suggestive, however, the definitive diagnosis is depended on the histological examination. Despite of being a benign tumor, it has a high risk of recurrence after conservative treatment. The potential risk for malignant is also present. Therefore, complete resection of the tumors is the treatment of choice. Conclusion: We herein present a report of a rare case with had a giant biliary cystadenoma (BCA) primary origin. This report aims to improve the understanding of the diagnosis and management of this uncommon disease.

Heteroleptic Triple-Stranded Metallosupramolecules with Hydrophobic Inner Voids.

The systematic combination of well-defined coordination spheres and multiple types of ligands (heteroleptic) can lead to the generation of hierarchical metallosupramolecules with a high level of complexity and functionality. In particular, a specific multilevel coordination-driven assembly through the initiate generation of multinuclear clusters can form unique heteroleptic multiple-stranded supramolecular complexes. Herein, we report novel triple-stranded nickel-based supramolecules constructed from two different ditopic ligands ([1,1':3',1''-terphenyl]-4,4''-dicarboxylate (TP) and 2,6-pyridinedicarboxylate (PDA)) and a nickel precursor. The solid-state structures of the as-synthesized supramolecules revealed that three PDA ligands are employed to fabricate a tetranuclear ({Ni4}) cluster, and two {Ni4} clusters are assembled to form the final triple-stranded metallosupramolecules by three TP ligands. The bridging TP ligands also provide large inner voids with highly hydrophobic environments. Structural investigation of the generated complexes provided a deeper understanding of the aspects driving the formation of heteroleptic supramolecules, which is crucial for the design of multiple-strands with desired morphologies and functionalities.

The Therapeutic Role of Nanoparticle Shape in Traumatic Brain Injury : An in vitro Comparative Study.

OBJECTIVE: To perform a comparative analysis of therapeutic effects associated with two different shapes of ceria nanoparticles, ceria nanorods (Ceria NRs) and ceria nanospheres (Ceria NSs), in an in vitro model of traumatic brain injury (TBI). METHODS: In vitro TBI was induced using six-well confluent plates by manually scratching with a sterile pipette tip in a 6×6-square grid. The cells were then incubated and classified into cells with scratch injury without nanoparticles and cells with scratch injury, which were treated separately with 1.16 mM of Ceria NSs and Ceria NRs. Antioxidant activities and anti-inflammatory effects were analyzed. RESULTS: Ceria NRs and Ceria NSs significantly reduced the level of reactive oxygen species compared with the control group of SH-SY5Y cells treated with Dulbecco's phosphate-buffered saline. The mRNA expression of superoxide dismutases was also reduced in nanoparticle-treated SH-SY5Y cells, but apparently the degree of mRNA expression decrease was not dependent on the nanoparticle shape. Exposure to ceria nanoparticles also decreased the cyclooxygenase-2 expression, especially prominent in Ceria NR-treated group than that in Ceria NS-treated group. CONCLUSION: Ceria nanoparticles exhibit antioxidant and anti-inflammatory effects in TBI models in vitro. Ceria NRs had better antiinflammatory effect than Ceria NSs, but showed similar antioxidant activity.

Gold nanodot assembly within a cobalt chalcogenide nanoshell: Promotion of electrocatalytic activity.

The assembly of functional nanoparticles within materials with unique architectures can improve the interfacial surfaces, defects, and active sites, which are key factors for the designing novel nanocatalysts. Nano metal-organic framework (NMOF) can be employed to fabricate nanodots-confined nanohybrids for use in electrocatalytic processes. Herein, we report a controlled synthesis of gold nanodot assembly within cobalt chalcogenide nanoshell (dots-in-shell Au/CoxSy nanohybrids). A cobalt-based NMOF (the cobalt-based zeolite imidazole framework, ZIF-67) is used as a versatile sacrificial template to yield dots-in-shell Au/CoxSy nanohybrids. Due to the synergistic effect of the well-dispersed Au nanodots and the thin CoxSy nanoshell, the obtained dots-in-shell Au/CoxSy nanohybrids exhibit enhanced performance for the oxygen evolution reaction (OER) with low overpotential values at a current density of 10 mA cm-2 and a small Tafel slope (343 mV and 62 mV dec-1, respectively).

Polyurethane Foam Incorporated with Nanosized Copper-Based Metal-Organic Framework: Its Antibacterial Properties and Biocompatibility.

Polyurethane foams (PUFs) have attracted attention as biomaterials because of their low adhesion to the wound area and suitability as biodegradable or bioactive materials. The composition of the building blocks for PUFs can be controlled with additives, which provide excellent anti-drug resistance and biocompatibility. Herein, nanosized Cu-BTC (copper(II)-benzene-1,3,5-tricarboxylate) was incorporated into a PUF via the crosslinking reaction of castor oil and chitosan with toluene-2,4-diisocyanate, to enhance therapeutic efficiency through the modification of the surface of PUF. The physical and thermal properties of the nanosized Cu-BTC-incorporated PUF (PUF@Cu-BTC), e.g., swelling ratio, phase transition, thermal gravity loss, and cell morphology, were compared with those of the control PUF. The bactericidal activities of PUF@Cu-BTC and control PUF were evaluated against Pseudomonas aeruginosa, Klebsiella pneumoniae, and methicillin-resistant Staphylococcus aureus. PUF@Cu-BTC exhibited selective and significant antibacterial activity toward the tested bacteria and lower cytotoxicity for mouse embryonic fibroblasts compared with the control PUF at a dose of 2 mg mL-1. The Cu(II) ions release test showed that PUF@Cu-BTC was stable in phosphate buffered saline (PBS) for 24 h. The selective bactericidal activity and low cytotoxicity of PUF@Cu-BTC ensure it is a candidate for therapeutic applications for the drug delivery, treatment of skin disease, and wound healing.

Photo-Thermal Switching of Individual Plasmonically Activated Spin Crossover Nanoparticle Imaged by Ultrafast Transmission Electron Microscopy.

Spin crossover (SCO) is a promising switching phenomenon when implemented in electronic devices as molecules, thin films or nanoparticles. Among the properties modulated along this phenomenon, optically induced mechanical changes are of tremendous importance as they can work as fast light-induced mechanical switches or allow to investigate and control microstructural strains and fatigability. The development of characterization techniques probing nanoscopic behavior with high spatio-temporal resolution allows to trigger and visualize such mechanical changes of individual nanoscopic objects. Here, ultrafast transmission electron microscopy (UTEM) is used to precisely probe the length changes of individual switchable nanoparticles induced thermally by nanosecond laser pulses. This allows revealing of the mechanisms of spin switching, leading to the macroscopic expansion of SCO materials. This study is conducted on individual pure SCO nanoparticles and SCO nanoparticles encapsulating gold nanorods that serve for plasmonic heating under laser pulses. Length changes are compared with time-resolved optical measurements performed on an assembly of these particles.

Shape effect of cerium oxide nanoparticles on mild traumatic brain injury.

The catalytic performance and therapeutic effect of nanoparticles varies with shape. Here, we investigated and compared the therapeutic outcomes of ceria nanospheres (Ceria NSs) and ceria nanorods (Ceria NRs) in an in vivo study of mild traumatic brain injury (mTBI). In vivo TBI was induced in a mouse model of open head injury using a stereotaxic impactor. Outcomes including cytoprotective effects, cognitive function, and cerebral edema were investigated after retro-orbital injection of 11.6 mM of ceria nanoparticles. Ceria nanoparticles significantly reduced fluoro-jade B (FJB)-positive cells and terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL)-positive cells, and restored mRNA levels of superoxide dismutase 1 (SOD1) and SOD2. They also decreased the cyclooxygenase-2 (COX-2) expression compared with the untreated control group. Comparing the two nanomaterials, Ceria NRs showed less stable and high-energy (100) and (110) planes, which increased the number of active sites. The Ce3+/Ce4+ molar ratio of Ceria NRs (0.40) was greater than that of Ceria NSs (0.27). Ceria NRs (0.059 ± 0.021) appeared to exhibit better anti-inflammatory effect than Ceria NSs (0.133 ± 0.024), but the effect was statistically insignificant (p = 0.190). Ceria nanoparticles also improved cognitive impairment following mTBI compared with the control group, but the effect did not differ significantly according to the nanoshape. However, Ceria NRs (70.1 ± 0.5%) significantly decreased brain water content compared with Ceria NSs (73.7 ± 0.4%; p = 0.0015), indicating a more effective reduction in brain edema (p = 0.0015). Compared with Ceria NSs, the Ceria NRs are more effective in alleviating cerebral edema following in vivo mTBI.

A 62-year-old man with stridor and dyspnoea.

Stridor is a sign of vital emergency that immediately orientates towards a laryngeal or tracheal obstruction. This case report focuses on the management of stridor, which comprises emergency securing of airways and parallel aetiological investigations. https://bit.ly/39CTjOg.

Recent advances in heteroleptic multiple-stranded metallosupramolecules.

Well-ordered combination of defined coordination spheres and multiple types of ligands (heteroleptic) in a given structure can expand the structural complexity and functional diversity of the resulting metallosupramolecules. Such heteroleptic metallosupramolecular architectures are expected to afford advanced utility in a variety of applications. In this concise review article, recent advances in the development of multi-nuclear-cluster-based heteroleptic multiple-stranded (HLMS) metallosupramolecules are summarized and demonstrated. To construct HLMS metallosupramolecules, one type of multitopic ligands can be employed for building up multiple strands, while another type of ligands can be utilized to construct multi-nuclear clusters. Most HLMS metallosupramolecules adopt helical geometries and have high molecular symmetry, which can be key factors for the structural completion. HLMS metallosupramolecules can be used as basic building blocks for the fabrication of higher-order polymeric or discrete assembly architectures with well-defined geometries.

Ameloblastic Carcinoma in a 2-Year-Old Child: A Case Report and Review of the Literature.

Ameloblastic carcinoma (AC) is a rare malignant odontogenic tumor in pediatric patients, only 22 cases have been reported in literature since 1932. We present an extremely rare case in which AC occurred in a 2-year-old girl, who had a tumor in the right mandible. Radiographic findings showed a multilocular, poorly defined, and mixed radiolucent-radiopaque lesion in the region of teeth #84 to #85, with bone and tooth root resorption. Computed tomography revealed buccal cortex destruction, tumor infiltration of soft tissue, and enlarged nodes. Incisional biopsy showed histomorphological features of AC. Immunohistochemical analysis exhibited a positive result for Cytokeratin (CK) 19 and overexpression of p53 and Ki67. The patient underwent right hemimandibulectomy and neck dissection. The final pathology was consistent with the initial diagnosis of AC. The patient did not exhibit signs of recurrence or metastasis within 2 years postoperatively. Given the rarity of this disease and the age of the patient, this report constitutes a valuable contribution to the current literature.

Effect of Ca(OH)2 dosing on thermophilic composting of anaerobic sludge to improve the NH3 recovery.

The primary biological treatment method for organic sludge is composting and/or anaerobic digestion, but their product (compost or biogas) is of little economic benefit; therefore, an improved process to produce a high-value product is required to make sludge management more sustainable. Maximizing NH3 gas recovery during composting processes has the potential benefit of producing high-value microalgal biomass. However, the majority of produced ammonia does not evaporate as NH3 gas but retains as NH4+-N in the compost after fermentation. The present study investigates the effects of the timing of Ca(OH)2 dosing (on days 2, 5, and 9), and the Ca(OH)2 dose (1.1-2.6 mmol/batch), on lab-scale thermophilic composting of anaerobic sludge. The effects on NH3 recovery, organic matter degradability, and microbial activity are evaluated. Ca(OH)2 dosing immediately improved the emission of NH3, with yields 50-69% higher than those under control conditions. The timing of the dosing did not influence NH3 recovery or organic matter degradability. Higher Ca(OH)2 doses resulted in higher NH3 recovery, while microbial activity was temporarily and marginally inhibited. The pH of the compost reached 10-11.5 but quickly dropped to 8-8.5 within a day, probably because of neutralization of Ca(OH)2 by the emitted CO2 and release of NH3, which maintained the microbial activity. The present study indicated that Ca(OH)2 dosing would be useful to apply during thermophilic composting for NH3 recovery to cultivate high-value microalgal biomass, which enables this process to obtain a more economic benefit.

Synthesis and Application of Dendritic Fibrous Nanosilica/Gold Hybrid Nanomaterials.

Morphologically unique silica nanoparticles can be used as effective templates to prepare silica-metal hybrid nanomaterials, which are highly applicable in a variety of areas. Mesoporous silica nanoparticles, which have high surface areas and an abundance of pores, can be used to synthesize mesoporous silica core-metal shell nanostructures with catalytically active sites. In this work, dendritic fibrous nanosilica (DFNS) with a high surface area is successfully employed as a template to synthesize DFNS/Au hybrid nanomaterials. Au nanodots are initially synthesized through the selective reduction of Au ions on the surface of the DFNS after surface modification to form DFNS/Au dots. A seed-mediated growth method is used to controllably grow Au nanoparticles on the DFNS/Au dots to generate DFNS core-Au nanoparticles shell nanohybrids (DFNS/Au NPs) and DFNS core-Au layer shell nanohybrids (DFNS/Au layers). The catalytic activities of DFNS/Au NPs and DFNS/Au layers in the 4-nitrophenol reduction reaction are compared.