Porous Cages Research Articles

Crystalline Metallo-Organic Cage by Triphenylene-Cored Hexaterpyridine for Fast Iodine Capture.

In recent years, radioactive iodine capture has played an important role in nuclear waste treatment. However, most of the adsorbents possess low economic efficiency and undesirable reutilization in practical application. In this work, a terpyridine-based porous metallo-organic cage was assembled for iodine adsorption. Through synchrotron X-ray analysis, the metallo-cage was found to have a porous hierarchical packing mode with inherent cavity and packing channel. By taking advantage of polycyclic aromatic units and charged ⟨tpy-Zn2+-tpy⟩ (tpy = terpyridine) coordination sites in the structure, this nanocage exhibits an excellent ability to capture iodine in both the gas phase and aqueous medium, and the crystal state of the nanocage shows an ultrafast kinetic process of capturing I2 in aqueous solution within 5 min. The calculated maximum sorption capacities for I2 based on the Langmuir isotherm models are 1731 and 1487 mg g-1 for amorphous and crystalline nanocages, which is noticeably higher than most of the reported iodine sorbent materials in the aqueous phase. This work not only provides a rare example of iodine adsorption by a terpyridyl-based porous cage but also expands the applications of terpyridine coordination systems into iodine capture.

Silicon nanosheets confined into nitrogen-doped porous carbon microcage enabling efficient lithium storage

Silicon (Si) is regarded as the promising next-generation commercial anode in high energy lithium-ion batteries (LIBs), attributed to its natural abundance, high theoretical capacity (4200 mAh g−1) and low voltage profile (<0.5 V). However, the huge volume change and tremendous capacity fading of silicon during lithiation/de-lithiation have been hindering its practical application. Herein, a facile and scalable method was proposed to prepare the Si nanosheets limited in 3D porous N-doped carbon micro cages (Si@NCM) particles with ternary oxygen-bridged covalent chemical bond, i.e., Si–O–C bonding. As a kind of anode materials, the Si@NCM rendered an extremely surprising reversible capacity of 930.2 mAh g−1 after 2000 cycles at a current density of 5 A g−1 at ambient temperature. More interestingly, it afforded an overwhelming capacity of 950.7 mAh g−1 after 3000 cycles at 20 A g−1 at 80 °C, with 89.8% capacity retention, and an excellent rate capability of 594.8 mAh g−1 at 50 A g−1. The impressive electrochemical performance was ascribed to its multi-scaled network structure and moderate covalent bonding, which enhanced Li+ diffusion kinetics and accommodated the volume expansion of the silicon. This simple fabrication approach holds great commercial possibility in practical application of next-generation advanced LIBs.

A biomimetic gradient porous cage with a micro-structure for enhancing mechanical properties and accelerating osseointegration in spinal fusion.

Spinal fusion is a widely employed treatment of patients with degenerative disc disease, in which a cage is used to replace the disc for spinal fusion. But it often fails for insufficient mechanical strength and poor osseointegration. Here, we designed a polyether-ether-ketone (PEEK)/tantalum (Ta) composite cage with a biomimetic gradient porous micro-structure, simultaneously enhancing mechanical properties and accelerating osseointegration in spinal fusion. In the study, based on the mechanical performances of PEEK and osteogenic potential of Ta, and the three-dimensional (3D) structures of cuttlebone and vertebra, the cages were respectively 3D printed by pure PEEK, PEEK with 5wt% Ta (PEEK/Ta-5), PEEK with 10wt% Ta (PEEK/Ta-10) and PEEK with 15wt% Ta (PEEK/Ta-15), then verified in vitro and in sheep cervical fusion model systematically. Vertebral Gyroid structure PEEK/Ta-15 cage exhibited superior mechanical properties than Cuttlebone-like structure PEEK/Ta-15 cage, closer to the cervical vertebra. Furthermore, PEEK/Ta-15 cage with higher Ta microparticles in PEEK provided a biomimetic gradient porous micro-structure with higher surface energy, guiding cell biological behavior, promoting new bone penetration, and accelerating osseointegration in vivo. In conclusion, the study designed a biomimetic gradient porous cage with a micro-structure for enhancing mechanical properties, accelerating osseointegration and forming an anatomical lock in the fusion segment through composites, mechanical efficiency, surface extension, and pores.

Biportal endoscopic extraforaminal lumbar interbody fusion using a 3D-printed porous titanium cage with large footprints: technical note and preliminary results.

The aim of this study was to introduce biportal endoscopic extraforaminal lumbar interbody fusion (BE-EFLIF), which involves insertion of a cage through a more lateral side as compared to the conventional corridor of transforaminal lumbar interbody fusion. We described the advantages and surgical steps of 3D-printed porous titanium cage with large footprints insertion through multi-portal approach, and preliminary results of this technique. This retrospective study included 12 consecutive patients who underwent BE-EFLIF for symptomatic single-level lumbar degenerative disease. Clinical outcomes, including a visual analog scale (VAS) for back and leg pain and the Oswestry disability index (ODI), were collected at preoperative months 1 and 3, and 6 months postoperatively. In addition, perioperative data and radiographic parameters were analyzed. The mean patient age, follow-up period, operation time, and volume of surgical drainage were 68.3 ± 8.4 years, 7.6 ± 2.8 months, 188.3 ± 42.4 min, 92.5 ± 49.6 mL, respectively. There were no transfusion cases. All patients showed significant improvement in VAS and ODI postoperatively, and these were maintained for 6 months after surgery (P < 0.001). The anterior and posterior disc heights significantly increased after surgery (P < 0.001), and the cage was ideally positioned in all patients. There were no incidences of early cage subsidence or other complications. BE-EFLIF using a 3D-printed porous titanium cage with large footprints is a feasible option for minimally invasive lumbar interbody fusion. This technique is expected to reduce the risk of cage subsidence and improve the fusion rate.

Porous Metal-Organic Cages Based on Rigid Bicyclo[2.2.2]oct-7-ene Type Ligands: Synthesis, Structure, and Gas Uptake Properties.

Three new ligands containing a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit have been used to assemble lantern-type metal-organic cages with the general formula [Cu4 L4 ]. Functionalisation of the backbone of the ligands leads to distinct crystal packing motifs between the three cages, as observed with single-crystal X-ray diffraction. The three cages vary in their gas sorption behaviour, and the capacity of the materials for CO2 is found to depend on the activation conditions: softer activation conditions lead to superior uptake, and one of the cages displays the highest BET surface area found for lantern-type cages so far.

Trabecular Bone Remodeling After Posterior Lumbar Interbody Fusion: Comparison of Three-Dimensional Porous Tantalum and Titanium-Coated Polyetheretherketone Interbody Cages.

Retrospective cohort study. The criteria for determining completion of intervertebral stability after posterior lumbar interbody fusion (PLIF) remain controversial. Several new radiological indicators of bone growth and osteointegration have been established. We compared computed tomography (CT) findings related to osteointegration after PLIF with interbody cages of two different materials and designs. We retrospectively analyzed data from 103 patients who underwent PLIF with three-dimensional porous tantalum (Tn) cages or titanium-coated polyetheretherketone (TiP) cages. CT images obtained 3months and 1year after surgery were examined for trabecular bone remodeling (TBR), cancellous condensation (CC), and vertebral endplate cyst (VEC) formation. The incidences of each finding were compared by cage type, and rates of instrument failure and pseudarthrosis were determined. Three months postoperatively, 87% of the levels with Tn cages exhibited TBR, whereas 96% of those with TiP cages did not (P < .001). Most levels with Tn cages levels exhibited TBR and no CC 3months (81%) and 1 year (94%) after surgery. Although 78% of levels with TiP cages exhibited CC and no TBR 3months after surgery, 59% exhibited both CC and TBR 1 year after surgery. Significantly fewer VECs formed around the Tn cages than around the TiP cages both 3months (P = .002) and 1year (P < .001) after surgery. Implant-related problems occurred at levels that exhibited neither TBR nor CC. The porous tantalum cage may enable intervertebral stability that is comparable to bony fusion soon after surgery.

Porous Salts as Platforms for Heterogeneous Catalysis.

The preparation of a new class of reactive porous solids, prepared via straightforward salt metathesis reactions, is described here. Reaction of the dimethylammonium salt of a magnesium-based porous coordination cage with the chloride salt of [CrII Cl(Me4 cyclam)]+ affords a porous solid with concomitant removal of dimethylammonium chloride. The salt consists of the ions combined in the expected ratio based on their charge as confirmed by UV-vis and X-ray photoelectron spectroscopies, ion chromatography (IC), and inductively coupled plasma mass spectrometry (ICP-MS). The porous salt boasts a Brunauer-Emmett-Teller (BET) surface area of 213m2 g-1 . Single crystal X-ray diffraction reveals the chromium(II) cations in the structure reside in the interstitial space between porous cages. Importantly, the chromium(II) centers, previously shown to react with O2 to afford reactive chromium(III)-superoxide adducts, are still accessible in the solid state as confirmed by UV-vis spectroscopy. The site-isolated reactive centers have competence toward hydrogen atom abstraction chemistry and display significantly increased stability and reactivity as compared to dissolved ions.

Bridging the Gap between Charge Storage Site and Transportation Pathway in Molecular-Cage-Based Flexible Electrodes.

Porous materials have been widely applied for supercapacitors; however, the relationship between the electrochemical behaviors and the spatial structures has rarely been discussed before. Herein, we report a series of porous coordination cage (PCC) flexible supercapacitors with tunable three-dimensional (3D) cavities and redox centers. PCCs exhibit excellent capacitor performances with a superior molecular capacitance of 2510 F mmol-1, high areal capacitances of 250 mF cm-2, and unique cycle stability. The electrochemical behavior of PCCs is dictated by the size, type, and open-close state of the cavities. Both the charge binding site and the charge transportation pathway are unambiguously elucidated for PCC supercapacitors. These findings provide central theoretical support for the "structure-property relationship" for designing powerful electrode materials for flexible energy storage devices.

Speed and quality of interbody fusion in porous bioceramic Al2O3 and polyetheretherketone cages for anterior cervical discectomy and fusion: a comparative study

BackgroundThe objective of this prospective randomized monocentric study is to compare the speed and quality of interbody fusion of implanted porous Al2O3 (aluminium oxide) cages with PEEK (polyetheretherketone) cages in ACDF (anterior cervical discectomy and fusion).Materials and methodsA total of 111 patients were enrolled in the study, which was carried out between 2015 and 2021. The 18-month follow-up (FU) was completed in 68 patients with an Al2O3 cage and 35 patients with a PEEK cage in one-level ACDF. Initially, the first evidence (initialization) of fusion was evaluated on computed tomography. Subsequently, interbody fusion was evaluated according to the fusion quality scale, fusion rate and incidence of subsidence.ResultsSigns of incipient fusion at 3 months were detected in 22% of cases with the Al2O3 cage and 37.1% with the PEEK cage. At 12-month FU, the fusion rate was 88.2% for Al2O3 and 97.1% for PEEK cages, and at the final FU at 18 months, 92.6% and 100%, respectively. The incidence of subsidence was observed to be 11.8% and 22.9% of cases with Al2O3 and PEEK cages, respectively.ConclusionsPorous Al2O3 cages demonstrated a lower speed and quality of fusion in comparison with PEEK cages. However, the fusion rate of Al2O3 cages was within the range of published results for various cages. The incidence of subsidence of Al2O3 cages was lower compared to published results. We consider the porous Al2O3 cage as safe for a stand-alone disc replacement in ACDF.

Static Analysis and Design of Innovative Porous Lumbar Interbody Cages

Background: Interbody discs play a major role in maintaining the spine and skeleton structures which may undergo damage. If damage is so severe that the disc cannot be repaired, implants, known as “interbody cages”, should be used. Objectives: The present study aimed to propose a novel design with proper strength and resistance against axial disc torques. Methods: The design and analysis of innovative anatomical cages comprised two stages, namely, cage design according to three different models and finite element analysis (FEA). The designs were based on the spine of a 15-year-old teenager without lumbar disc disease. To model the vertebrae, computed tomography )CT( scans and Digital Imaging and Communications in Medicine (DICOM) files were entered into Mimics Version 10.01 (Materialise Inc., Leuven, Belgium); then, the L4 and L5 spinal segments were modeled. Results: The implants were fixed to the bottom level and subjected to a net force of 1000 N. Additionally, a moment load of 7.5 Nm in flexion, extension, axial rotation, and lateral bending was applied in these three cage models. Considering the application of 1000-N force, maximum and minimum stress and strain distribution rates were presented in three honeycomb, Islamic architecture, and porous gyroid cages. Conclusion: Novel designs for lumbar cages were considered to achieve damping capacity, light weight, and high resistance. Considering the characteristics of the honeycomb, Islamic architecture, and gyroid structures, optimal designs were proposed for lumbar cages to achieve adequate strength and resistance against axial disc torques under normal conditions.

Vertebral Endplate Concavity in Lateral Lumbar Interbody Fusion: Tapered 3D-Printed Porous Titanium Cage versus Squared PEEK Cage

Background and Objectives: To prevent postoperative problems in extreme lateral interbody fusion (XLIF), it is critical that the vertebral endplate not be injured. Unintentional endplate injuries may depend on the cage. A novel porous titanium cage for XLIF has improved geometry with a tapered tip and smooth surface. We hypothesized that this new cage should lead to fewer endplate injuries. Materials and Methods: This retrospective study included 32 patients (mean 74.1 ± 6.7 years, 22 females) who underwent anterior and posterior combined surgery with XLIF for lumbar degenerative disease or adult spinal deformity from January 2018 to June 2022. A tapered 3D porous titanium cage (3DTi; 11 patients) and a squared PEEK cage (sPEEK; 21 patients) were used. Spinal alignment values were measured on X-ray images. Vertebral endplate concavity (VEC) was defined as concavity ≥ 1 mm of the endplate on computed tomography (CT) images, which were evaluated preoperatively and at 1 week and 3 months postoperatively. Results: There were no significant differences in the patient demographic data and preoperative and 3-month postoperative spinal alignments between the groups. A 3DTi was used for 25 levels and an sPEEK was used for 38 levels. Preoperative local lordotic angles were 4.3° for 3DTi vs. 4.7° for sPEEK (p = 0.90), which were corrected to 12.3° and 9.1° (p = 0.029), respectively. At 3 months postoperatively, the angles were 11.6° for 3DTi and 8.2° for sPEEK (p = 0.013). VEC was present in 2 levels (8.0%) for 3DTi vs. 17 levels (45%) for sPEEK (p = 0.002). After 3 months postoperatively, none of the 3DTi had VEC progression; however, eight (21%) levels in sPEEK showed VEC progression (p = 0.019). Conclusions: The novel 3DTi cage reduced endplate injuries by reducing the endplate load during cage insertion.

Resourcelized conversion of livestock manure to porous cage microsphere for eliminating emerging contaminants under peroxymonosulfate trigger

Pollution and resource waste caused by the improper disposal of livestock manure, and the threat from the release of emerging contaminants (ECs), are global challenges. Herein, we address the both problems simultaneously by the resourcelized conversion of chicken manure into porous Co@CM cage microspheres (CCM-CMSs) for ECs degradation through the graphitization process and Co-doping modification step. CCM-CMSs exhibit excellent performance for ECs degradation and actual wastewater purification under peroxymonosulfate (PMS) initiation, and show adaptability to complex water environments. The ultra-high activity can maintain after continuous operation over 2160 cycles. The formation of C-O-Co bond bridge structure on the catalyst surface caused an unbalanced electron distribution, which allows PMS to trigger the sustainable electron donation of ECs and electron gain of dissolved oxygen processes, becoming the key to the excellent performance of CCM-CMSs. This process significantly reduces the resource and energy consumption of the catalyst throughout the life cycle of production and application.

Mechanical performance of porous biomimetic intervertebral body fusion devices: an in vitro biomechanical study

BackgroundDegenerative disc disease is one of the most common ailments severely affecting the quality of life in elderly population. Cervical intervertebral body fusion devices are utilized to provide stability after surgical intervention for cervical pathology. In this study, we design a biomimetic porous spinal cage, and perform mechanical simulations to study its performances following American Society for Testing and Materials International (ASTM) standards before manufacturing to improve design process and decrease cost and consumption of material.MethodsThe biomimetic porous Ti-6Al-4 V interbody fusion devices were manufactured by selective laser melting (laser powder bed fusion: LPBF in ISO/ASTM 52900 standard) and subsequently post-processed by using hot isostatic pressing (HIP). Chemical composition, microstructure and the surface morphology were studied. Finite element analysis and in vitro biomechanical test were performed.FindingsThe post heat treatment can optimize its mechanical properties, as the stiffness of the cage decreases to reduce the stress shielding effect between two instrumented bodies. After the HIP treatment, the ductility and the fatigue performance are substantially improved. The use of HIP post-processing can be a necessity to improve the physical properties of customized additive manufacturing processed implants.InterpretationIn conclusion, we have successfully designed a biomimetic porous intervertebral device. HIP post-treatment can improve the bulk material properties, optimize the device with reduced stiffness, decreased stress shielding effect, while still provide appropriate space for bone growth.Clinical significanceThe biomechanical performance of 3-D printed biomimetic porous intervertebral device can be optimized. The ductility and the fatigue performance were substantially improved, the simultaneously decreased stiffness reduces the stress shielding effect between two instrumented bodies; while the biomimetic porous structures provide appropriate space for bone growth, which is important in the patients with osteoporosis.

Monitoring the Solution Persistence of Porous Coordination Cages with Diffusion NMR Spectroscopy and Cryogenic Transmission Electron Microscopy

As a unique class of molecular adsorbents, porous coordination cages (PCCs) have garnered interest because of their potential solubility, which enables applications not available to activated carbons, zeolites, metal–organic frameworks (MOFs), and covalent organic frameworks (COFs), such as covalent membrane incorporation, solution-based ion binding, and facile incorporation into porous liquids. The identification of key aspects of cage behavior in solution such as the self-assembly process, structural integrity in solution, conformational changes, and cage interactions with guest molecules is necessary to broaden the utility of soluble porous cages. Many characterization strategies for permanently porous coordination cages have been limited to the solid state and have relied heavily on X-ray diffraction, electron microscopy, and infrared (IR), UV–vis, and nuclear magnetic resonance (NMR) spectroscopies. As such, definitive evidence of cage behavior while in solution has been lacking, as the often-paramagnetic nature of permanently porous coordination cages complicates one-dimensional NMR spectroscopy experiments. Here, we explore the combined use of diffusion-ordered spectroscopy NMR (DOSY NMR), transmission electron microscopy (TEM), and cryogenic transmission electron microscopy (cryo-TEM) to confirm the persistence of soluble PCCs in various solutions.

Retrospective Case Series of Porous Titanium Cages in Oblique Lumbar Interbody Fusion Surgery Assessing Subsidence, Fusion and Functional Outcomes

Purpose: Implant subsidence is a possible complication of spinal interbody fusion. We aim to evaluate porous titanium cages subsidence, fusion and functional outcomes in patients subjected to oblique lumbar interbody fusion (OLIF) with these novel devices. Methods: Our institutional review board approved a single-center experience which included 60 patients who underwent OLIF from June 2018 to June 2020 utilizing the porous titanium implants. Data was collected in accordance with the Declaration of Helsinki, and written informed consent was obtained. Imaging studies including radiographs 1, 3, 6 and 12 months and computed tomography (CT) scan at 6 months obtained during routine postoperative follow-up visits, were studied for signs of implant subsidence, fusion and clinical parameters to determine the effectiveness of surgery such as Oswestry disability index (ODI). Results: Radiographic subsidence occurred in 1 out of 89 porous titanium interbody cages (1.1%). No subsidence was observed in the posterior screws and rods fixation group (N = 57). However, one case of subsidence occurred in the lateral plate fixation group (N = 3). The subsidence occurred in an osteoporotic elderly patient operated for adjacent segment disease, and she was later revised with posterior instrumentation using cemented screws and rods. She had an uneventful recovery. Fusion rates were evaluated under CT scan at 6 months with a rate of 88%. In terms of clinical outcomes, ODI decreased significantly from 20.3 preop to 10.7 postop with a P-value < 0.05. Conclusions: In our study, the subsidence rate was lower than previously reported in the literature. Also, we had good fusion rates at 6 months likely due to the porous titanium cages use. We had no subsidence in the posterior instrumented group and one case in the lateral fixation group with improved clinical outcomes.

Recent advances in porous molecular cages for photocatalytic organic conversions.

Photocatalytic organic conversion is considered an efficient, environmentally friendly, and energy-saving strategy for organic synthesis. In recent decades, the molecular cage has emerged as a creative functional material with broad applications in host-guest recognition, drug delivery, catalysis, intelligent materials and other fields. Based on the unique properties of porous molecular cage materials, they provide an ideal platform for leveraging pre-structuring in catalytic reactions and show great potential in various photocatalytic organic reactions. As a result, they have emerged as promising alternatives to conventional molecules or inorganic photocatalysts in redox processes. In this Review, the synthesis strategies based on coordination cages and organic cages, as well as their recent progress in photocatalytic organic conversion, are comprehensively summarized. Finally, we deliver the persistent challenges associated with porous molecular cage compounds that need to be overcome for further development in this field.

Rapid post-synthetic modification of porous coordination cages with copper-catalyzed click chemistry.

Novel cobalt calixarene-capped and zirconium-based porous coordination cages were prepared with alkyne and azide functionality to leverage post-synthetic modification by click chemistry. While the calixarene-capped cages showed impressive stability when exposed to the most straightforward copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction conditions with copper(II) sulfate and sodium ascorbate as the reducing agent, milder reaction conditions were necessary to perform analogous CuAAC reactions on zirconium-based cages. Reaction kinetics were monitored by IR spectroscopy, confirming rapid reaction times (<3 hours).

Metalloporphyrin modified defective TiO2 porous cages with the enhanced photocatalytic activity for coupling of hydrogen generation and tetracycline removal.

Integration of molecular transition-metal complexes and semiconductors is an appealing method to develop high-performance hybrid photocatalysts based on improvement of their solar energy harvesting ability and photogenerated charge carrier separation efficiency. Herein, Cu-TCPP modified TiO2 porous cages with oxygen vacancy defects, derived from NH2-MIL-125(Ti) nanocrystals, are successfully prepared to form PC-TiO2-d/Cu-TCPP hybrids via a surface assembly process. The PC-TiO2-d/Cu-TCPP hybrid shows an enhanced photodegradation efficiency (73.7%, 95.4%) towards tetracycline in the air under visible light or the simulated sunlight irradiation compared to PC-TiO2-d (33.7%, 81.1%) within 100 min. Moreover, the photocatalytic system is applicable to coupling both processes of solar fuel production and pollutant degradation. The PC-TiO2-d/Cu-TCPP hybrid exhibits a high hydrogen evolution rate of ∼2 mmol g-1 h-1 in the aqueous solution of tetracycline in an inert atmosphere upon irradiation by the simulated sunlight. In contrast, an inferior photocatalytic performance of hydrogen evolution is observed in pure water without the addition of tetracycline. Finally, the high sustainability of PC-TiO2-d/Cu-TCPP is mainly attributed to the strong interaction between the molecular photosensitizer and the semiconductor photocatalyst by oxygen vacancies and Cu(ii) ions.

The marriage of porous cages and metal clusters for advanced catalysis

This review summaries the latest advances in synthetic strategies and characterization techniques of cage-encapsulated metal clusters. We highlight the advantages that emerge from the synergistic combination of porous cages and metal clusters in catalytic applications.

Facile synthesis of layered double hydroxide nanosheets assembled porous structures for efficient drug delivery.

As one of the important types of two-dimensional materials, layered double hydroxides (LDHs) have been widely used in the biomedical field as carriers for drug delivery. In this case, we propose a facile synthetic method for preparing LDH-based self-assembly structures via a metal ions-mediated zeolitic imidazolate framework-8 (ZIF-8) transformation process. The as-made hierarchical porous ZIF-8@LDHs core-shell structures and porous cages of LDHs (PC-LDHs) in drug delivery systems are used to study the loading and release of small molecular weight drugs such as doxorubicin hydrochloride (DOX) and 5-fluorouracil (5-FU). The intrinsic properties and assembly structures of both carriers are investigated in depth for their impact on slow drug release. Finally, PC-LDHs outperform ZIF-8@LDHs core-shell structures in terms of drug delivery performance under various conditions, indicating that LDH nanosheets would play a decisive role in the drug delivery process. In the drug release system, scattered LDH nanosheets with smaller sizes than their assemblies are gradually produced, allowing nanodrugs to enter cancer tissues more easily across biological barriers. This study provides the preliminary preparation for an LDH-based nanomedicine platform in the field of cancer therapy.