The dynamic ethylene adsorption on carbon xerogels as a three-way game between porosity, surface chemistry and humidity.

Novel carbon xerogels doped with heteroatoms (O, N, S) were prepared by sol-gel polymerization of resorcinol with heterocyclic aldehydes containing them. All doped materials presented higher O-contents than the reference material prepared with formaldehyde, and significant S- or N-loadings in the corresponding samples. Carbon xerogels were micro-mesoporous and N-doping favoured the formation of mesopores. Their efficiency in the dynamic ethylene adsorption is presented as an interplay between porosity, surface chemistry and humidity. The surface hydrophilicity was also studied by water adsorption assays, a quick adsorption being favoured in microporous samples with hydrophilic O-groups. Breakthrough curves for ethylene adsorption were recorded in both dry and humid conditions and analysed according to the mass transference zone (MTZ). The material behaviour was correlated with the physicochemical properties, elucitating the mechanism of the simultaneous water/ethylene adsorption. The adsorption capacity depended linearly on the microporous characteristics of samples; however, MTZ parameters (efficiency of the column) varied linearly with the electronegativity of the dopant element. Both doping and humidity in the stream hindered the ethylene adsorption kinetic and capacity (up to 33% for N-doped material under humidity compared to undoped-material under dry conditions), due to reduced adsorbate-adsorbent interactions and the accessibility into narrow pores.

Tetrahedral DNA Framework-Based Spherical Nucleic Acids for Efficient siRNA Delivery.

Spherical nucleic acids (SNAs) hold substantial therapeutic potential for the delivery of small interfering RNAs (siRNAs). Nevertheless, their potential remains largely untapped due to the challenges of cytosolic delivery. Inspired by the dynamic, spiky architecture of coronavirus, an interface engineering approach based on a tetrahedral DNA framework (tDF) is demonstrated for the development of coronavirus-mimicking SNAs. By exploiting their robustness and precise construction, tDFs are evenly arranged on the surface of core nanoparticles (NPs) with flexible conformations, generating a dynamic, spiky architecture. This spiky architecture in tetrahedral DNA framework-based SNAs (tDF-SNAs) substantially improve siRNAs duplex efficiency from 20% to 95%. Meanwhile, tDF-SNAs changed the endocytosis pathway to clathrin-independent cellular engulfment pathway and enhanced the cellular uptake efficiency. Due to these advances, the delivery efficiency of siRNA molecules by tDF-SNAs is 1-2 orders of magnitude higher than that of SNAs, resulting in a 2-fold increase in gene silencing efficacy. These results show promise in the development of bioinspired siRNAs delivery systems for intracellular applications.

Physicochemical Modulations in MXenes for Carbon Dioxide Mitigation and Hydrogen Generation: Tandem Dialogue between Theoretical Anticipations and Experimental Evidences.

The dawn of MXenes has fascinated researchers under their intriguing physicochemical attributes that govern their energy and environmental applications. Modifications in the physicochemical properties of MXenes pave the way for efficient energy-driven operations such as carbon capture and hydrogen generation. The physicochemical modulations such as interface engineering through van der Waals coupling with homo/hetero-junctions render the tunability of optoelectronic variables driving the photochemical and electrochemical processes. Herein, we have reviewed the recent achievements in physicochemical properties of MXenes by highlighting the role of intercalants/terminal groups, atomic defects, surface chemistry and few/mono-layer formation. Recent findings of MXenes-based materials are systematically surveyed in a tandem manner with the future outlook for constructing next-generation multi-functional catalytic systems. Theoretical modelling of MXenes surface engineering proffers the mechanistic comprehension of surface phenomena such as termination, interface formation, doping and functionalization, thereby enabling the researchers to exploit them for targeted applications. Therefore, theoretical anticipations and experimental evidences of electrochemical/photochemical carbon dioxide reduction and hydrogen evolution reactions are synergistically discussed.

Adsorbate Resonance Induces Water-Metal Bonds in Electrochemical Interfaces.

This study delves into the intricate interactions between surface-near species, OH and H2O, on electrodes in electrochemical interfaces. These species are an inevitable part of many electrocatalytic energy conversion reactions such as the oxygen reduction reaction. In our modeling, we utilize high statistics on a dataset of complex solid solutions with high atomic variability to show the emergence of H2O-metal covalent bonds under specific conditions. Based on density functional theory (DFT) calculations of adsorption energies on many thousands of different surface compositions, we provide a quantifiable physical understanding of this induced water covalency, which is rooted in simple quantum mechanics. Directional hydrogen bonding between surface-near H2O and OH, enables surface bonding electrons to delocalize mediated by near-symmetrical adsorbate resonance structures. The different adsorbate resonance structures differ by surface coordination explaining the induced H2O-metal bonding.

Tuning interfacial molecular asymmetry to engineer protective coatings with superior surface anchoring, antifouling and antibacterial properties.

Multifunctional robust protective coatings that combine biocompatibility, antifouling and antimicrobial properties play an essential role in reducing host reactions and infection on invasive medical devices. However, developing these protective coatings generally faces a paradox: coating materials capable of achieving robust adhesion to substrates via spontaneous deposition inevitably initiate continuous biofoulant adsorption, while those employing strong hydration capability to resist biofoulant attachment have limited substrate binding ability and durability under wear. Herein, we designed a multifunctional terpolymer of poly(dopamine methyacrylamide-co-2-methacryloyloxyethyl phoasphorylcholine-co-2-(dimethylamino)-ethyl methacrylate) (P(DMA-co-MPC-co-DMAEMA)), which integrates desired yet traditionally incompatible functions (i.e., robust adhesion, antifouling, lubrication, and antimicrobial properties). Direct normal and lateral force measurements, dynamic adsorption tests, surface ion conductance mapping were applied to comprehensively investigate the nanomechanics of coating-biofloulant interactions. Catechol groups of DMA act as basal anchors for robust substrate deposition, while the highly hydrated zwitterion of MPC provides apical protection to resist biofouling and wear. Moreover, the antimicrobial property is conferred through the protonation of tertiary amine groups on DMAEMA, inhibiting infection under physiological conditions. This work provides an effective strategy for harmonizing demanded yet incompatible properties in one coating material, with significant implications for the development of multifunctional surfaces towards the advancement of invasive biomedical devices. STATEMENT OF SIGNIFICANCE: Multifunctional robust protective coatings have been widely utilized in invasive medical devices to mitigate host responses and infection. However, modified surface coatings often encounter a trade-off between robust adhesion to substrates and strong hydration capability for antifouling and antimicrobial properties. We propose a universal strategy for surface modification by dopamine-assisted co-deposition with a multifunctional terpolymer of P(DMA-co-MPC-co-DMAEMA) that simultaneously achieves robust adhesion, antifouling, and antimicrobial properties. Through elucidating the nanomechanics with fundamentally understanding the interactions between the coating and biomacromolecules, we highlight the role of DMA for substrate adhesion, MPC for biofouling resistance, and DMAEMA for antimicrobial activity. This approach presents a promising strategy for constructing multifunctional coatings on minimally invasive medical devices by tuning interfacial molecular asymmetricity to reconcile incompatible properties within one coating.

Directing Organometallic Ring-Chain Equilibrium by Electrostatic Interactions.

Dynamic chemistry, which falls into the realm of both supramolecular and covalent chemistry, enables intriguing properties, such as structural diversity, self-healing, and adaptability. Due to robustness of covalent bonds compared to noncovalent ones, dynamic covalent chemistry has been exploited to synthesize complex molecular nanostructures at solid/liquid interfaces under ambient conditions, generally responsive to internal factors that directly regulate intermolecular covalent bonds. However, directing dynamics of covalent nanostructures, e.g., the typical ring-chain equilibria, on surface by extrinsic interactions remains elusive and challenging. Herein, we have controllably directed the ring-chain equilibrium of covalent organometallic structures by regulating intermolecular electrostatic interactions, thus achieving on-surface dynamic covalent chemistry under ultrahigh vacuum conditions. Our findings unravel the dynamic mechanism of covalent polymers governed by weak intermolecular interactions at the submolecular level, which not only bridges the gap between supramolecular and covalent chemistry but also offers great opportunities for the fabrication of adaptive polymeric nanostructures that respond to different conditions.

Tailorable Fluorescent Perovskite Quantum Dots for Multiform Manufacturing via Two-Step Thiol-Ene Click Chemistry.

In practical applications, fluorescent perovskite quantum dots (PQDs) must exhibit high efficiency, stability, and processibility. So far, it remains a challenge to synthesize PQDs with stable dispersibility in tailorable monomers both before and after photocuring. In this work, a novel strategy of UV-induced two-step thiol-ene "click chemistry" is proposed to prepare PQDs with these attributes. The first step aims to epitaxially grow a shell around the PQD core to ensure stable dispersibility in a thiol-ene monomer solution. The second step is to achieve stable dispersibility in the photocured thiol-ene matrixes for multiform manufacturing processes. The tailorable PQDs (T-PQDs) not only have the highest photoluminescence quantum yield (PLQY) to ≈100% for green emission and over 96% for red emission, but also exhibit remarkable stability under severe conditions, including "double 85" aging, water exposure, and mechanical stress. Moreover, their exceptional processability allows for various processing techniques, including slot-die coating, inkjet printing, direct-laser writing, UV-light 3D printing, nanoimprinting, and spin coating. The high efficiency and stability of T-PQDs facilitate their multiform manufacturing for a wide range of applications.

Can Carbon be Used as an Anode for Water Splitting?

Carbon materials, whose structural and electronic properties can be fine-tuned, are promising material solutions for many energy-related systems. However, due to the lack of fundamental understanding of the carbon surface chemistry, especially when they are used in electrolytes, the rapid development of carbon as electrodes has led to many widely accepted misunderstandings. Focusing on the case of carbon-based electrode for water splitting, this Viewpoint tries to highlight the main problems of the area and demonstrates/presents the dynamic carbon surface chemistry in the application. The role of carbon as an anode for water splitting is revealed and if it can be practically used in water splitting is discussed.

Surface Ligands for Perovskite Quantum Dots.

The combination of the quantum confinement effect of quantum dots (QDs) and unique photoelectric properties of perovskite semiconductors make perovskite quantum dots (PQDs) a promising candidate for photoelectric devices. To truly unlock their potential, a deep understanding of structure-property relationship is paramount. Among the various factors influencing this relationship, the role of surface ligands cannot be overstated. The polarity, conductivity, stability, and interaction effects of these ligands with QD surfaces create complicated ligand-QDs relationships, which greatly influences the successful synthesis of QDs. In essence, the surface chemistry of ligands serves as a critical determinant in shaping the properties of both the resulting QDs and QD-based devices. To address this, our paper introduces an innovative approach to studying ligands, utilizing their inherent functional groups as a classification criterion. It is begun by discussing the types of surface defects of PQDs and the functional groups used for passivation, emphasizing the importance of analyzing ligands based on their functional groups. Then the passivation mechanisms of ligands with various functional groups and their impact on enhancing QD performance are delved into. Ultimately, this paper summarizes and offers several design principles and rules for PQDs surface ligands that can be applied in most scenarios.

Surface Chemistry of a Halogenated Borazine: From Supramolecular Assemblies to a Random Covalent BN-Substituted Carbon Network.

The on-surface synthesis strategy has emerged as a promising route for fabricating well-defined two-dimensional (2D) BN-substituted carbon nanomaterials with tunable electronic properties. This approach relies on specially designed precursors and requires a thorough understanding of the on-surface reaction pathways. It promises precise structural control at the atomic scale, thus complementing chemical vapor deposition (CVD). In this study, we investigated a novel heteroatomic precursor, tetrabromoborazine, which incorporates a BN core and an OH group, on Ag(111) using low temperature scanning tunnelling microscopy/spectroscopy (LT-STM/STS) and X-ray photoelectron spectroscopy (XPS). Through sequential temperature-induced reactions involving dehalogenation and dehydrogenation, distinct tetrabromoborazine derivatives were produced as reaction intermediates, leading to the formation of specific self-assemblies. Notably, the resulting intricate supramolecular structures include a chiral kagomé lattice composed of molecular dimers exhibiting a unique electronic signature. The final product obtained was a random covalent carbon network with BN-substitution and embedded oxygen heteroatoms. Our study offers valuable insights into the significance of the structure and functionalization of BN precursors in temperature-induced on-surface reactions, which can help future rational precursor design. Additionally, it introduces complex surface architectures that offer a high areal density of borazine cores.

Metal-Free Wet Chemistry for the Fast Gram-Scale Synthesis of γ-Graphyne and its Derivatives.

γ-Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal-free nucleophilic crosslinking method using wet chemistry for fast gram-scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro-(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as-prepared GY reveals a layered structure, characterized by the presence of the C(sp)-C(sp2) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F-/N-rich GY derivatives, using electron-deficient fluoro-substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal-free, scalable, and cost-effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials.

Advancements in π-Magnetism and Precision Engineering of Carbon-Based Nanostructures.

The emergence of π-magnetism in low-dimensional carbon-based nanostructures, such as nanographenes (NGs), has captured significant attention due to their unique properties and potential applications in spintronics and quantum technologies. Recent advancements in on-surface synthesis under ultra-high vacuum conditions have enabled the atomically precise engineering of these nanostructures, effectively overcoming the challenges posed by their inherent strong chemical reactivity. This review highlights the essential concepts and synthesis methods used in studying NGs. It also outlines the remarkable progress made in understanding and controlling their magnetic properties. Advanced characterization techniques, such as scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM), have been instrumental in visualizing and manipulating these nanostructures, which highlighting their critical role in the field. The review underscores the versatility of carbon-based π-magnetic materials and their potential for integration into next-generation electronic devices. It also outlines future research directions aimed at optimizing their synthesis and exploring applications in cutting-edge technologies.

Modifying the Reactivity of Single Pd Sites in a Trimetallic Sn-Pd-Ag Surface Alloy: Tuning CO Binding Strength.

Improving control over active-site reactivity is a grand challenge in catalysis. Single-atom alloys (SAAs) consisting of a reactive component doped as single atoms into a more inert host metal feature localized and well-defined active sites, but fine tuning their properties is challenging. Here, a framework is developed for tuning single-atom site reactivity by alloying in an additional inert metal, which this work terms an alloy-host SAA. Specifically, this work creates about 5% Pd single-atom sites in a Pd33Ag67(111) single crystal surface, and then identifies Sn based on computational screening as a suitable third metal to introduce. Subsequent experimental studies show that introducing Sn indeed modifies the electronic structure and chemical reactivity (measured by CO desorption energies) of the Pd sites. The modifications to both the electronic structure and the CO adsorption energies are in close agreement with the calculations. These results indicate that the use of an alloy host environment to modify the reactivity of single-atom sites can allow fine-tuning of catalytic performance and boost resistance against strong-binding adsorbates such as CO.

Unlocking Self-antioxidant Capability and Processability of Additive-free MXene Ink towards High-performance Customizable Supercapacitors.

The solution processing of MXene ink is the feasible strategy to realize its state-of-the-art applications. Nevertheless, achieving high stability and processability of additive-free MXene ink is particularly challenging. Herein, we propose an oxyanion-terminated Ti3C2Tx MXene ink that exhibits excellent self-antioxidant capability and processability. The vertex-connected polyhedrons of oxyanions capping on the Ti3C2 host serve as an in-situ antioxidative shield, effectively preventing the attack of free H2O molecules while increasing the robustness of the Ti-C bond and reducing the susceptibility of surface Ti atoms to oxidation. Consequently, the shelf life of MXene ink can be extended up to 5 months at room temperature. Moreover, the high electron accumulation of oxyanions enhances the interlayer interactions among MXene sheets through electrostatic binding, which enables the formation of stable and uniform MXene inks with controlled rheological properties and processability. Inspired by Chinese calligraphy, we utilize the oxyanion-terminated MXene ink to fabricate high-performance and customizable paper supercapacitors, which exhibit exceptional flexibility and stability, allowing them to be tailored to desired capacity, stretchability, and shapes. This in-situ surface chemistry strategy of oxyanion can activate the self-antioxidant capability and solution processability of MXene, paving the way for its widespread applications in flexible and wearable electronics.

Synthesis, Surface Chemistry, and Applications of Non-Zero-Dimensional Diamond Nanostructures.

Diamond nanomaterials are renowned for their exceptional properties, which include the inherent attributes of bulk diamond. Additionally, they exhibit unique characteristics at the nanoscale, including high specific surface areas, tunable surface structure, and excellent biocompatibility. These multifaceted attributes have piqued the interest of researchers globally, leading to an extensive exploration of various diamond nanostructures in a myriad of applications. This review focuses on non-zero-dimensional (non-0D) diamond nanostructures including diamond films and extended diamond nanostructures, such as diamond nanowires, nanoplatelets, and diamond foams. It delves into the fabrication, modification, and diverse applications of non-0D diamond nanostructures. This review begins with a concise review of the preparation methods for different types of diamond films and extended nanostructures, followed by an exploration of the intricacies of surface termination and the process of immobilizing target moieties of interest. It then transitions into an exploration of the applications of diamond films and extended nanostructures in the fields of biomedicine and electrochemistry. In the concluding section, this article provides a forward-looking perspective on the current state and future directions of diamond films and extended nanostructures research, offering insights into the opportunities and challenges that lie ahead in this exciting field.

Surface Chemistry Induced IgG Unfolding and Modulation of Immune Responses.

Immunoglobulin G (IgG) comprises a significant portion of the protein corona that forms on biomaterial surfaces and holds a pivotal role in modulating host immune responses. To shed light on the important relationship between biomaterial surface functionality, IgG adsorption, and innate immune responses, we prepared, using plasma deposition, four surface coatings with specific chemistries, wettability, and charge. We found that nitrogen-containing coatings such as these deposited from allylamine (AM) and 2-methyl-2-oxazoline (POX) cause the greatest IgG unfolding, while hydrophilic acrylic acid (AC) surfaces allowed for the retention of the protein structure. Structural changes in IgG significantly modulated macrophage attachment, migration, polarization, and the expression of pro- and anti-inflammatory cytokines. Unfolded IgG on the POX and AM surfaces enhanced macrophage attachment, migration, extracellular trap release, and pro-inflammatory factors production such as IL-6 and TNF-α. Retention of IgG structure on the AC surface downregulated inflammatory responses. The findings of this study demonstrate that the retention of protein structure is an essential factor that must be taken into consideration when designing biomaterial surfaces. Our study indicates that using hydrophilic surface coatings could be a promising strategy for designing immune-modulatory biomaterials for clinical applications.

Improved Properties of Glass Vials for Primary Packaging with Atomic Layer Deposition.

Novel pharmaceuticals and drug delivery devices may require better performance from the packaging material e.g., in terms of extractables and leachables, and unwanted interactions. To address this, we applied atomic layer deposition (ALD) to build nanometer-range SiO2, ZrO2 and Al2O3-TiO2 films on primary packaging glass. Controlled modification of the surface also enabled creation of functionality without affecting visual appearance of the material. ALD-coated Type I borosilicate vials were compared to uncoated ones, and tailored functionality was presented by appropriate measurements. The tested ALD coatings formed a barrier on glass against extractables and leachables, from the vial and the coating alike. A good ALD coating prevents any leakage into the stored drug product. Hydrolytic resistance results improved by 85-92 %, and these results correlated well with straightforward water conductivity measurements. Opposite to uncoated borosilicate glass vials, no extracted elements could be detected from the extracts of the coated vials with stable ALD films. Improved surface integrity was observed with electron microscopy as well. ALD films increased hydrophilicity of the surface and tuning the ALD film thickness and composition allowed precise blocking of UV light wavelengths, without affecting transparency. As a conclusion, ALD is a versatile method to create barrier and functional films on primary packaging materials.

Surface Coating of Nickel-Titanium (Ni-Ti) Pediatric Rotary File Using Graphene Oxide: A Scanning Electron Microscopy Analysis.

BACKGROUND: The effectiveness of endodontic files relies significantly on the characteristics of the outermost layer, which can be greatly improved through suitable surface treatments and appropriate coatings. Graphene-based materials (GBMs) have been utilized to fabricate nanocomposite coatings aimed at improving surface characteristics and mechanical behavior, including resilience, sustainability, oxidation resistance, solidity, and traction. AIM: This research aims to study the surface topography of a nickel-titanium (Ni-Ti) pediatric rotary file coated with graphene oxide (GO) using a scanning electron microscope (SEM). METHODS: The study utilized Ni-Ti pediatric rotary instruments that were 16 mm long and had the same ISO tip size of #25. The Ni-Ti pediatric rotary files had a titanium oxide coating that needed to be removed for the application of the GO coating. The GO coating was applied to the files using an electrophoretic deposition (EPD) procedure. Data were gathered to evaluate the surface topography and structural profiles of the GO-coated endodontic files through SEM analysis. RESULTS: SEM imaging showed that the GO coatings consisted of numerous layers of GO sheets, which were uniformly and thoroughly applied to the endodontic instrument. A substantial portion of the GO layers aligned with neighboring layers along the edges, creating a continuous structure. CONCLUSION: GO coatings were effectively applied to Ni-Ti endodontic instruments using EPD. The deposition of the GO coating is consistent throughout the surface of the Ni-Ti rotary instrument.

Endothelium-Mimicking Materials: A "Rising Star" for Antithrombosis.

The advancement of antithrombotic materials has significantly mitigated the thrombosis issue in clinical applications involving various medical implants. Extensive research has been dedicated over the past few decades to developing blood-contacting materials with complete resistance to thrombosis. However, despite these advancements, the risk of thrombosis and other complications persists when these materials are implanted in the human body. Consequently, the modification and enhancement of antithrombotic materials remain pivotal in 21st-century hemocompatibility studies. Previous research indicates that the healthy endothelial cells (ECs) layer is uniquely compatible with blood. Inspired by bionics, scientists have initiated the development of materials that emulate the hemocompatible properties of ECs by replicating their diverse antithrombotic mechanisms. This review elucidates the antithrombotic mechanisms of ECs and examines the endothelium-mimicking materials developed through single, dual-functional and multifunctional strategies, focusing on nitric oxide release, fibrinolytic function, glycosaminoglycan modification, and surface topography modification. These materials have demonstrated outstanding antithrombotic performance. Finally, the review outlines potential future research directions in this dynamic field, aiming to advance the development of antithrombotic materials.

Schottky Diode Leakage Current Fluctuations: Electrostatically Induced Flexoelectricity in Silicon.

Nearly four decades have passed since IBM scientists pioneered atomic force microscopy (AFM) by merging the principles of a scanning tunneling microscope with the features of a stylus profilometer. Today, electrical AFM modes are an indispensable asset within the semiconductor and nanotechnology industries, enabling the characterization and manipulation of electrical properties at the nanoscale. However, electrical AFM measurements suffer from reproducibility issues caused, for example, by surface contaminations, Joule heating, and hard-to-minimize tip drift and tilt. Using as experimental system nanoscale Schottky diodes assembled on oxide-free silicon crystals of precisely defined surface chemistry, it is revealed that voltage-dependent adhesion forces lead to significant rotation of the AFM platinum tip. The electrostatics-driven tip rotation causes a strain gradient on the silicon surface, which induces a flexoelectric reverse bias term. This directional flexoelectric internal-bias term adds to the external (instrumental) bias, causing both an increased diode leakage as well as a shift of the diode knee voltage to larger forward biases. These findings will aid the design and characterization of silicon-based devices, especially those that are deliberately operated under large strain or shear, such as in emerging energy harvesting technologies including Schottky-based triboelectric nanogenerators (TENGs).