Facile Modification Research Articles

Structural Regulation of Covalent Organic Frameworks for Catalysis.

ConspectusChemical reactions can be promoted at lower temperatures and pressures, thereby reducing the energy input, by introducing suitable catalysts. Despite its significance, the quest for efficient and stable catalysts remains a significant challenge. In this context, addressing the efficiency of catalysts stands out as a paramount concern. However, the challenges posed by the vague structure and limited tailorability of traditional catalysts would make it highly desirable to fabricate optimized catalysts based on the understanding of structure-activity relationships. Covalent organic frameworks (COFs), a subclass of fully designed crystalline materials formed by the polymerization of organic building blocks through covalent bonds have garnered widespread attention in catalysis. The precise and customizable structures of COFs, coupled with attributes such as high surface area and facile functional modification, make COFs attractive molecular platforms for catalytic applications. These inherent advantages position COFs as ideal catalysts, facilitating the elucidation of structure-performance relationships and thereby further improving the catalysis. Nevertheless, there is a lack of systematic emphasis on and summary of structural regulation at the atomic/molecular level for COF catalysis. Consequently, there is a growing need to summarize this research field and provide deep insights into COF-based catalysis to promote its further development.In this Account, we will summarize recent advances in structural regulation achieved in COF-based catalysts, placing an emphasis on the molecular design of the structures for enhanced catalysis. Considering the unique components and structural advantages of COFs, we present the fundamental principles for the rational design of structural regulation in COF-based catalysis. This Account starts by presenting an overview of catalysis and explaining why COFs are promising catalysts. Then, we introduce the molecular design principle for COF catalysis. Next, we present the following three aspects of the specific strategies for structural regulation of COF-based catalysts: (1) By designing different functional groups and integrating metal species into the organic unit, the activity and/or selectivity can be finely modulated. (2) Regulating the linkage facilitates charge transfer and/or modulates the electronic structure of catalytic metal sites, and accordingly, the intrinsic activity/selectivity can be further improved. (3) By means of pore wall/space engineering, the microenvironment surrounding catalytic metal sites can be modulated to optimize performance. Finally, the current challenges and future developments in the structural regulation of COF-based catalysts are discussed in detail. This Account provides insight into the structural regulation of COF-based catalysts at the atomic/molecular level toward improving their performance, which would provide significant inspiration for the design and structural regulation of other heterogeneous catalysts.

Facile superhydrophobic modification on HPMC film using polydimethylsiloxane and starch granule coatings

The excessive water sensitivity of hydroxypropyl methylcellulose (HPMC) films prevent them from being used extensively. In order to overcome this limitation, superhydrophobic HPMC films were meticulously crafted through the utilization of a composite of polydimethylsiloxane (PDMS) and ball-milled rice starch, corn starch, or potato starch (RS/CS/PS) for the coating process. Initially possessing hydrophilic properties, the HPMC Film (CA = 49.3 ± 1.8°) underwent a transformative hydrophobic conversion upon the application of PDMS, resulting in a static contact angle measuring up to 103.4 ± 2.0°. Notably, the synergistic combination of PDMS-coated HPMC with ball-milled starch demonstrated exceptional superhydrophobic attributes. Particularly, the treated HPMC-based film, specifically the HP-CS-2 h film, showcased an impressive contact angle of 170.5° alongside a minimal sliding angle of 5.2°. The impact of diverse starch types and the ball milling treatment on the PDMS/starch coatings and HPMC film was thoroughly examined using scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXS), and particle size analysis. These studies demonstrated that the low surface energy and roughness required for the creation of superhydrophobic HPMC-based films were imparted by the hierarchical structure formed by the application of PDMS/ball-milled starch. Chemical compounds studied in this articlePolydimethylsiloxane (PubChem CID: 24764); Hydroxypropyl methylcellulose (PubChem CID: 671); Ethyl acetate (PubChem CID: 8857).

Defect engineering enables an advanced separator modification for high-performance lithium-sulfur batteries

High-energy–density lithium-sulfur batteries have been rated as a promising, yet challenging, next-generation battery technology. Typically, the serious shuttle of polysulfide intermediates and sluggish solid–solid reaction kinetics often result in irreversibly sulfur loss, low Coulombic efficiency, and limited lifespan. Herein, we propose a facile and efficient separator modification strategy using a rationally designed sulfiphilic and lithiophilic mediator, i.e. in-situ confinement growth of oxygen-deficient TiO2-x nanoparticles within nitrogen-doped mesoporous carbon matrix to modulate the sulfur electrochemistry. The nanoscale defective catalyst within open mesoporous host affords favorable adsorption of polysulfides and catalytic conversion ability. Moreover, the versatile composite improves the electrolyte wettability and Li+ transfer kinetics and alleviates self-discharge behavior. Resultantly, the Li-S batteries using modified separator achieves significantly improved cycling stability with a low capacity decay of only 0.067% per cycle after 500 cycles at 2C. The defect engineering together with separator modification strategies enable efficient and durable Li-S batteries.

Advancements of the Molecular Directed Design and Structure-Activity Relationship of Ferritin Nanocage.

Ferritin nanocages possess remarkable structural properties and biological functions, making them highly attractive for applications in functional materials and biomedicine. This comprehensive review presents an overview of the molecular characteristics, extraction and identification of ferritin, ferritin receptors, as well as the advancements in the directional design of high-order assemblies of ferritin and the applications based on its unique structural properties. Specifically, this Review focuses on the regulation of ferritin assembly from one to three dimensions, leveraging the symmetry of ferritin and modifications on key interfaces. Furthermore, it discusses targeted delivery of nutrition and drugs through facile loading and functional modification of ferritin. The aim of this Review is to inspire the design of micro/nano functional materials using ferritin and the development of nanodelivery vehicles for nutritional fortification and disease treatment.

Expanded bentonite clay by bio-adhesive resins and its impact on the mechanical, adhesion, and ultrasonic properties of NR/SBR/polyester cords systems

The improvement of the compatibility between two nonpolar rubber blends has a pivotal role to obtain superior blend properties. In this work, we utilized a facile and biofriendly modification approach of natural bentonite (BT) clay by two renewable resins, namely antibacterial gum rosin (GR) and soybean long oil alkyd resin (LAR). Which are considered to be toxicity-free reinforcing substance, thus preserving the bio-character of the substance. They used to increase the interlayer spacing distance between the BT galleries. This was proven by XRD and FT-IR. Natural rubber (NR)/styrene-butadiene rubber (SBR) blend was loaded with variable proportions of EBT-based GR and LAR bio-resins ranging from 3 to 15 wt.%. The ultrasonic and tensile properties were used to assess the compatibility between the rubber blends. The outcomes revealed that NR/SBR-3EBT-GR and NR/SBR-15EBT-LAR nanocomposites possessed higher tensile strength and rapture at break. Furthermore, the proposed mechanism of EBT by GR and LAR bio-resins with NR/SBR blend was studied. The both nanocomposites were then subjected to different measurements such as morphology by SEM and TEM, H-pull-out adhesion between rubber blends and polyester (PET) cords, and antibacterial activity. These new filled blend systems can be effective supporting a wide range of potential applications such as green tubeless tires technologies.

Activated nanosulfur for broad-spectrum heavy metals capture

Current problems of existing heavy metal-removing technologies, especially for nanomaterials-based ones, are typically single metal ion-specific, high-cost and collected difficult. Herein, facile modification of commercial sulfur creates a versatile adsorbent platform to address challenges. The versatile adsorbent can be easily prepared through solvothermal treatment of a saturated commercial sulfur solution, followed by water precipitation on a commercial foam that eliminates the need for separation. Interestingly, the solvothermal treatment endows the resulting nanosulfur with sulfate acid groups (hard Lewis base), sulfur anions (soft base), and sulfite groups (borderline base), promising the coordination of all types of heavy metal ions (Lewis acids). As such, this versatile adsorbent with well-distributed adsorption sites exhibits highly effective heavy metal adsorption capacity towards diverse heavy metal ions for both single-component and multi-component adsorption, including soft, hard, borderline Lewis metal ions, with ultra-high adsorption ability (e.g., 903.79 mg g−1 for Cu2+). These findings highlighted the potential of this low-cost sulfur-based adsorbent to address the arising challenges in ensuring clean water.

Improved Pb(II) removal by D001 resin with a facile nanoscale α-FeOOH modification

Macroporous strong acidic resin (D001) is restricted in Pb(II) removal from water due to the interference of common environmental cations. A novel modified D001 (nFeOOH@D001) was developed by loading nanoscale α-FeOOH (nFeOOH) with a facile ethanol-dispersion-impregnation method to improve Pb(II) removal from aqueous solution. Solid-phase analysis showed that α-FeOOH of 10–100 nm was evenly loaded onto D001. The nFeOOH@D001 maintained the electrostatic adsorption ability of D001, and obtained the complexation adsorption capacity of nFeOOH. The nFeOOH@D001 therefore achieved a 20.2% higher Pb(II) removal rate of 74.5% as compared to the D001 of 54.3%. Under the competition of Ca2+ and Mg2+ ions, the nFeOOH@D001 showed better selectivity for Pb(II) through the complexation of hydroxyl and ferrite groups on nFeOOH. The pseudo-first order kinetics and Langmuir-adsorption models well fitted the Pb(II) removal data, indicating a chemistry and monolayer adsorption process. This process depended on pH and achieved a Pb(II) removal over 65% within a pH range of 3–7. During cyclic test, used nFeOOH@D001 could be refreshed with acetic acid as eluent. Spent nFeOOH@D001 could be remodified with nFeOOH by the above impregnation method after stripping iron oxides with hydrochloric acid. The regenerated nFeOOH@D001 obtained a regeneration rate of 97.6% as compared to virginal nFeOOH@D001. The results demonstrated that the introduction of nFeOOH could effectively improve the performance of D001 for Pb(II) removal from water.

Thermoresponsive Gels with Embedded Starch Microspheres for Optimized Antibacterial and Hemostatic Properties.

Apart from single hemostasis, antibacterial and other functionalities are also desirable for hemostatic materials to meet clinical needs. Cationic materials have attracted great interest for antibacterial/hemostatic applications, and it is still desirable to explore rational structure design to address the challenges in balanced hemostatic/antibacterial/biocompatible properties. In this work, a series of cationic microspheres (QMS) were prepared by the facile surface modification of microporous starch microspheres with a cationic tannic acid derivate, the coating contents of which were adopted for the first optimization of surface structure and property. Thermoresponsive gels with embedded QMS (F-QMS) were further prepared by mixing a neutral thermosensitive polymer and QMS for second structure/function optimization through different QMS and loading contents. In vitro and in vivo results confirmed that the coating content plays a crucial role in the hemostatic/antibacterial/biocompatible properties of QMS, but varied coating contents of QMS only lead to a classical imperfect performance of cationic materials. Inspiringly, the F-QMS-4 gel with an optimal loading content of QMS4 (with the highest coating content) achieved a superior balanced in vitro hemostatic/antibacterial/biocompatible properties, the mechanism of which was revealed as the second regulation of cell-material/protein-material interactions. Moreover, the optimal F-QMS-4 gel exhibited a high hemostatic performance in a femoral artery injury model accompanied by the easy on-demand removal for wound healing endowed by the thermoresponsive transformation. The present work offers a promising approach for the rational design and facile preparation of cationic materials with balanced hemostatic/antibacterial/biocompatible properties.

Aptamer Technologies in Neuroscience, Neuro-Diagnostics and Neuro-Medicine Development.

Aptamers developed using in vitro Systematic Evolution of Ligands by Exponential Enrichment (SELEX) technology are single-stranded nucleic acids 10-100 nucleotides in length. Their targets, often with specificity and high affinity, range from ions and small molecules to proteins and other biological molecules as well as larger systems, including cells, tissues, and animals. Aptamers often rival conventional antibodies with improved performance, due to aptamers' unique biophysical and biochemical properties, including small size, synthetic accessibility, facile modification, low production cost, and low immunogenicity. Therefore, there is sustained interest in engineering and adapting aptamers for many applications, including diagnostics and therapeutics. Recently, aptamers have shown promise as early diagnostic biomarkers and in precision medicine for neurodegenerative and neurological diseases. Here, we critically review neuro-targeting aptamers and their potential applications in neuroscience research, neuro-diagnostics, and neuro-medicine. We also discuss challenges that must be overcome, including delivery across the blood-brain barrier, increased affinity, and improved in vivo stability and in vivo pharmacokinetic properties.

Facile surface modification of the poly(l-cysteine) on 2D-printed reduced graphene oxide electrode to fabricate a highly sensitive electrochemical sensor for determining the antipsychotic drug olanzapine

Amino acid-based polymers are alternative modifiers for electrode surface modification that can be simply and rapidly synthesized through electrochemical methods. Hence, we aim to develop a novel and easy-to-construct electrochemical sensor based on a two-dimensional-printed reduced graphene oxide electrode modified with poly(l-cysteine) for the determination of the antipsychotic drug olanzapine. The poly(l-cysteine) was employed as the only modifier for electrode surface modification, which was conducted via a single-step electropolymerization procedure. The surface composition and morphology of the developed sensor were examined by using a field emission scanning electron microscope, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The electrochemical characterization of the sensor was also performed by utilizing cyclic voltammetric and electrochemical impedance spectroscopic techniques. All electrochemical parameters and analytical performances of interest were thoroughly investigated. Under optimal conditions, the developed approach showed broad linear dynamic ranges of 10–1000 and 1500–5000 nM and a low detection limit of 0.91 nM in the detection of trace amounts of olanzapine. When the proposed approach was used to analyze olanzapine in human serum samples to verify its feasibility, it exhibited high accuracy and good precision. In contrast to conventional electrodes, our newly developed electrochemical electrode could be an appropriate device for monitoring the effectiveness and safety of the antipsychotic drug olanzapine.

Synergistic effect on dispersion, thermal conductivity and mechanical performance of pyrene modified boron nitride nanotubes with Al2O3/epoxy composites

Due to the intrinsic attributes of boron nitride nanotubes (BNNT), its assimilation into composite materials displays an immense potential for thermal performance augmentation. However, the presence of Van der Waals forces and hydrophobicity of BNNT causing interfacial incompatibility with the polymeric matrix greatly hinders its practical applications. This instigates a dispersion dilemma and subsequent agglomeration of BNNT in the polymer matrix, which massively hampers the thermal performance of the polymer composites. In this respect, we here present a facile BNNT modification strategy; deposition of amine-attached pyrene (PAA) on the BNNT surface through a mild sonication process. The presence of amine in the pyrene molecules reduces the surface tension of PAA deposited BNNT (BNNT-PAA) allowing it to be readily dispersed in the various solvents even at the high concentrations. BNNT-PAA was added as a co-filler along with a primary filler (Al2O3) in the epoxy resin. The formed epoxy composites presented an improvement of as much as 33.1 % in tensile strain and 175.8 % in tensile stress with the addition of 1wt% of BNNT-PAA, while the thermal conductivity of vertical direction was enhanced as high as 62.3 %, possibly due to the constructed BNNT thermal conducting channels among alumina particles.

Toward highly-robust MXene hybrid memristor by synergetic ionotronic modification and two-dimensional heterojunction

MXene is an emerging two-dimensional (2D) nanomaterial composed of several atomic layers of transition metal carbide/nitride/carbonitride. Due to its metal-analogous conductivity and rich surface functional groups, the facile surface modification of MXene is promising for extending its functionality into semiconductors. However, the application of surface-modulated MXene in robust memristor devices remains rarely reported. Here, the organic dye of celestine blue with conjugated skeleton and ionic interaction is employed to modify MXene, which succeeds to serve as the switching element in memristor device with synergetic ionotronic (ionic–electronic) property. Moreover, the device affords highly-robust performance through rational 2D sandwich heterojunction design. The underlying mechanism is elaborately clarified by theoretical charge transport modelling and experimental scanning electron microscopy analysis. This study sheds light on the prospect of high-performance MXene-based memristors through ionotronic modification strategy and provides efficient guidelines for broadening the application of novel 2D nanomaterials in non-volatile memory.

Unique Method for Facile Postsynthetic Modification of Nonisocyanate Polyurethanes.

Nonisocyanate polyurethanes (NIPUs) are broadly investigated as a potential replacement for conventional polyurethanes (PUs) to eliminate the use of toxic isocyanates and reduce occupational hazards. One of the most popular approaches to NIPU synthesis is the polyaddition of cyclic bis(carbonate)s and diamines to form poly(hydroxyurethane)s (PHUs). However, such PHUs are highly hydrophilic due to the presence of two hydroxyl groups per repeat unit, and the resulting moisture absorption significantly degrades their thermomechanical performance and physical stability upon exposure to humidity, thus limiting their utility. Here, we introduce a simple and scalable approach for the modification of PHUs to increase hydrophobicity and adjust their properties. The proposed reaction between aldehydes and appropriately spaced hydroxyl groups in the polymer backbone resulted in high degrees of modification (up to 84%) and up to 3-fold reductions in water uptake at 85% RH. Furthermore, the use of aromatic aldehydes in particular enabled the retention of mechanical properties over a wide range of humidity levels, resulting in performance comparable to conventional PUs. Finally, we note that this approach is not limited to reducing moisture sensitivity alone and provides ample opportunities for imparting a broad range of novel properties to PHUs through an appropriate selection of functional aldehydes.

Oxalate modification enabled advanced phosphate removal of nZVI: In Situ formed surface ternary complex and altered multi-stage adsorption process

Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.

A Facile Surface Modification Scheme for Medical-Grade Titanium and Polypropylene Using a Novel Mussel-Inspired Biomimetic Polymer with Cationic Quaternary Ammonium Functionalities for Antibacterial Application.

Medical device-associated infection remains a critical problem in the healthcare setting. Different clinical- or device-related methods have been attempted to reduce the infection rate. Among these approaches, creating a surface with bactericidal cationic functionality has been proposed. To do so, a sophisticated multi-step chemical procedure would be needed. Instead, a simple immersion approach was utilized in this investigation to render the titanium and polypropylene surface with the quaternary ammonium functionality by using a mussel-inspired novel lab-synthesized biomimetic catechol-terminated polymer, PQA-C8. The chemical oxidants, CuSO4/H2O2, as well as dopamine, were added into the novel PQA-C8 polymer immersion solution for one-step surface modification. Additionally, a two-step immersion scheme, in which the polypropylene substrate was first immersed in the dopamine solution and then in the PQA-C8 solution, was also attempted. Surface analysis results indicated the surface characteristics of the modified substrates were affected by the immersion solution formulation as well as the procedure utilized. The antibacterial assay has shown the titanium substrates modified by the one-step dopamine + PQA-C8 mixtures with the oxidants added and the polypropylene modified by the two-step scheme exhibited bacterial reduction percentages greater than 90% against both Gram-positive S. aureus and Gram-negative E. coli and these antibacterial substrates were non-cytotoxic.

The economic burden of Ebola virus disease: a review and recommendations for analysis

Background Ebola virus disease (EVD) continues to be a major public health threat globally, particularly in the low-and-middle-income countries (LMICs) of Africa. The social and economic burdens of EVD are substantial and have triggered extensive research into prevention and control. We aim to highlight the impact and economic implications, identify research gaps, and offer recommendations for future economic studies pertaining to EVD. Method We conducted a comprehensive librarian-led search in PubMed/Medline, Embase, Google Scholar, EconLit and Scopus for economic evaluations of EVD. After study selection and data extraction, findings on the impact and economics of EVD were synthesized using a narrative approach, while identifying gaps, and recommending critical areas for future EVD economic studies. Results The economic evaluations focused on the burden of illness, vaccine cost-effectiveness, willingness-to-pay for a vaccine, EVD funding, and preparedness costs. The estimated economic impact of the 2014 EVD outbreak in Guinea, Liberia, and Sierra Leone across studies ranged from $30 billion to $50 billion. Facility construction and modification emerged as significant cost drivers for preparedness. The EVD vaccine demonstrated cost-effectiveness in a dynamic transmission model; resulting in an incremental cost-effectiveness ratio of about $96 per additional disability adjusted life year averted. Individuals exhibited greater willingness to be vaccinated if it incurred no personal cost, with a minority willing to pay about $1 for the vaccine. Conclusions The severe impact of EVD puts pressure on governments and the international community for better resource utilization and re-allocation. Several technical and methodological issues related to economic evaluation of EVD remain to be addressed, especially for LMICs. We recommend conducting cost-of-sequelae and cost-of-distribution analyses in addition to adapting existing economic analytical methods to EVD. Characteristics of the affected regions should be considered to provide evidence-based economic plans and economic-evaluation of mitigations that enhance resource allocation for prevention and treatment.

Preparation of sodium alginate encapsulated anionic polyacrylamide microcapsules with delayed thickening performance

Polyacrylamide (PAM) is a polymer compound that is widely used in oil extraction, wastewater treatment, food processing and other fields. As a typical polymer flooding agent, PAM has received much attention in the field of oil extraction due to its unique of viscoelastic properties. However, polymer flooding faces several challenges in oil reservoirs, including high injection pressure, high shear loss and crossflow. In an effort to overcome this challenge, we designed a method of coating Ca2+ cross-linked sodium alginate onto the core structure of polyacrylamide, providing shear resistance and sustained release performance for the polymer. The important role of the shell material was indirectly demonstrated by measuring its apparent viscosity using digital rotary viscometer. Moreover, the swelling behavior of microcapsules in water was observed using an optical microscope. The protective shell made the slow release of anionic PAM into water under stirring at 500 rpm, maintaining the viscosity of the fluid below 10 mPa·s within 2 h, and the viscosity increased from 1.8 mPa·s to 30 mPa·s after 35 h. In addition, this work revealed the importance of effective encapsulation by emulsification/external gelation method and a facile shell modification by the layer-by-layer self-assembly method.

Facile Graphene Oxide Modification Method via Hydroxyl-yne Click Reaction for Ultrasensitive and Ultrawide Monitoring Pressure Sensors.

Enhancing the durability and functionality of existing materials through sustainable pathways and appropriate structural design represents a time- and cost-effective strategy for the development of advanced wearable devices. Herein, a facile graphene oxide (GO) modification method via the hydroxyl-yne click reaction is present for the first time. By the click coupling between propiolate esters and hydroxyl groups on GO under mild conditions, various functional molecules are successfully grafted onto the GO. The modified GO is characterized by FTIR, XRD, TGA, XPS, and contact angle, proving significantly improved dispersibility in various solvents. Besides the high efficiency, high selectivity, and mild reaction conditions, this method is highly practical and accessible, avoiding the need for prefunctionalizations, metals, or toxic reagents. Subsequently, a rGO-PDMS sponge-based piezoresistive sensor developed by modified GO-P2 as the sensitive material exhibits impressive performance: high sensitivity (335 kPa-1, 0.8-150 kPa), wide linear range (>500 kPa), low detection limit (0.8 kPa), and long-lasting durability (>5000 cycles). Various practical applications have been demonstrated, including body joint movement recognition and real-time monitoring of subtle movements. These results prove the practicality of the methodology and make the rGO-PDMS sponge-based pressure sensor a real candidate for a wide array of wearable applications.

High yield and wide lateral size growth of α-Mo2C: exploring the boundaries of CVD growth of bare MXene analogues

Synthesis of Mo2C bare MXenes, without surface terminations groups, via chemical vapor deposition (CVD) on metal foils is scientifically a very intriguing crystal growth process, and there are still challenges and limited fundamental understanding to overcome to obtain high yield and wide crystal size lateral growth. Achieving large area coverage via direct growth is scientifically vital to utilize the full potential of their unique properties in different applications. In this study, we sought to expand the boundaries of the current CVD growth approach for Mo2C MXenes and gain insights into the possibilities and limitations of large area growth, with a particular focus on controlling Mo concentration. We report a facile modification of their typical CVD growth protocol and show its influence on the Mo2C synthesis, with growth times spanning up to 3 h. Specifically, prior to initiating the CVD growth process, we introduced a holding step in temperature at 1095 °C. This proved to be beneficial in increasing the Mo concentration on the liquid Cu growth surface. We achieved an average Mo2C crystals coverage of approximately 50% of the growth substrate area, increased tendency of coalescence and merging of individual flakes, and lateral flake sizes up to 170 μm wide. To gain deeper understanding into their CVD growth behavior, we conducted a systematic investigation of the effect of several factors, including (i) a holding step time on Mo diffusion rate through molten Cu, (ii) the Cu foil thickness over the Mo foil, and (iii) the CVD growth time. Phase, chemical and microstructural characterization by x-ray diffraction, x-ray photon spectroscopy, SEM and scanning/transmission electron microscopy revealed that the grown crystals are single phase α-Mo2C. Furthermore, insights gained from this study sheds light on crucial factors and inherent limitations that are essential to consider and may help guide future research progress in CVD growth of bare MXenes.

Pillararene-Based Stimuli-Responsive Supramolecular Delivery Systems for Cancer Therapy.

Cancer poses a significant challenge to global public health, seriously threatening human health and life. Although various therapeutic strategies, such as chemotherapy (CT), radiotherapy, phototherapy, and starvation therapy, are applied to cancer treatment, their limited therapeutic effect, severe side effects, and unsatisfactory drug release behavior need to be carefully considered. Thus, there is an urgent need to develop efficient drug delivery strategies for improving cancer treatment efficacy and realizing on-demand drug delivery. Notably, pillararenes, as an emerging class of supramolecular macrocycles, possess unique properties of highly tunable structures, superior host-guest chemistry, facile modification, and good biocompatibility, which are widely used in cancer therapy to achieve controllable drug release and reduce the toxic side effects on normal tissues under various internal/external stimuli conditions. This review summarizes the recent advance of stimuli-responsive supramolecular delivery systems (SDSs) based on pillararenes for tumor therapy from the perspectives of different assembly methods and hybrid materials, including molecular-scale SDSs, supramolecular nano self-assembly delivery systems, and nanohybrid SDSs. Moreover, the prospects and critical challenges of stimuli-responsive SDSs based on pillararenes for cancer therapy are also discussed.