Hybrid organic-inorganic structures trigger the formation of primitive cell-like compartments.

Alkaline hydrothermal vents have become a candidate setting for the origins of life on Earth and beyond. This is due to several key features including the presence of gradients of temperature, redox potential, pH, the availability of inorganic minerals, and the existence of a network of inorganic pore spaces that could have served as primitive compartments. Chemical gardens have long been used as experimental proxies for hydrothermal vents. This paper investigates-10pc]Please note that the spelling of the following author name in the manuscript differs from the spelling provided in the article metadata: Richard J. G. Löffler. The spelling provided in the manuscript has been retained; please confirm. a set of prebiotic interactions between such inorganic structures and fatty alcohols. The integration of a medium-chain fatty alcohol, decanol, within these inorganic minerals, produced a range of emergent 3 dimensions structures at both macroscopic and microscopic scales. Fatty alcohols can be considered plausible prebiotic amphiphiles that might have assisted the formation of protocellular structures such as vesicles. The experiments presented herein show that neither chemical gardens nor decanol alone promote vesicle formation, but chemical gardens grown in the presence of decanol, which is then integrated into inorganic mineral structures, support vesicle formation. These observations suggest that the interaction of fatty alcohols and inorganic mineral structures could have played an important role in the emergence of protocells, yielding support for the evolution of living cells.

Carbon dots fluorescence can be used to distinguish isobaric peptide and to monitor protein oligomerization dynamics.

Carbon dots (CD) are widely investigated particles with interesting fluorescent properties which are reported to be used for various purposes, as they are biocompatible, resistant to photobleaching and with tuneable properties depending on the specific CD surface chemistry. In this work, we report on the possibility to use opportunely designed CD to distinguish among isobaric peptides almost undistinguishable by mass spectrometry, as well as to monitor protein aggregation phenomena. Particularly, cell-penetrating peptides containing the carnosine moiety at different positions in the peptide chain produce sequence specific fluorescent signals. Analogously, different insulin oligomerization states can also be distinguished by the newly proposed experimental approach. The latter is here described in details and can be potentially applied to any kind of peptide or protein.

Surface chemistry engineered selenium nanoparticles as bactericidal and immuno-modulating dual-functional agents for combating methicillin-resistant Staphylococcus aureus Infection.

Because of the extremely complexed microenvironment of drug-resistant bacterial infection, nanomaterials with both bactericidal and immuno-modulating activities are undoubtedly the ideal modality for overcoming drug resistance. Herein, we precisely engineered the surface chemistry of selenium nanoparticles (SeNPs) using neutral (polyvinylpyrrolidone-PVP), anionic (letinan-LET) and cationic (chitosan-CS) surfactants. It was found that surface chemistry greatly influenced the bioactivities of functionalized SeNPs, their interactions with methicillin-resistant Staphylococcus aureus (MRSA), immune cells and metabolisms. LET-functionalized SeNPs with distinct metabolisms exhibited the best inhibitory efficacy compared to other kinds of SeNPs against MRSA through inducing robust ROS generation and damaging bacterial cell wall. Meanwhile, only LET-SeNPs could effectively activate natural kill (NK) cells, and enhance the phagocytic capability of macrophages and its killing activity against bacteria. Furthermore, in vivo studies suggested that LET-SeNPs treatment highly effectively combated MRSA infection and promoted wound healing by triggering much more mouse NK cells, CD8+ and CD4+ T lymphocytes infiltrating into the infected area at the early stage to efficiently eliminate MRSA in the mouse model. This study demonstrates that the novel functionalized SeNP with dual functions could serve as an effective antibacterial agent and could guide the development of next generation antibacterial agents.

Wide-field optical imaging of electrical charge and chemical reactions at the solid-liquid interface.

From molecules and particles to macroscopic surfaces immersed in fluids, chemical reactions often endow interfaces with electrical charge which in turn governs surface interactions and interfacial phenomena. The ability to measure the electrical properties of a material immersed in any solvent, as well as to monitor the spatial heterogeneity and temporal variation thereof, has been a long-standing challenge. Here, we describe an optical microscopy-based approach to probe the surface charge distribution of a range of materials, including inorganic oxide, polymer, and polyelectrolyte films, in contact with a fluid. The method relies on optical visualization of the electrical repulsion between diffusing charged probe molecules and the unknown surface to be characterized. Rapid image-based measurements enable us to further determine isoelectric points of the material as well as properties of its ionizable chemical groups. We further demonstrate the ability to optically monitor chemically triggered surface charge changes with millisecond time resolution. Finally, we present a scanning-surface probe technique capable of diffraction-limited imaging of spatial heterogeneities in chemical composition and charge over large areas. This technique will enable facile characterization of the solid-liquid interface with wide-ranging relevance across application areas from biology to engineering.

Phenylacetylene-Terminated Poly(Ethylene Glycol) as Ligands for Colloidal Noble Metal Nanoparticles: a New Tool for "Grafting to" Approach.

We report a new design of polymer phenylacetylene (PA) ligands and the ligand exchange methodology for colloidal noble metal nanoparticles (NPs). PA-terminated poly(ethylene glycol) (PEG) can bind to metal NPs through acetylide (M-C≡C-R) that affords a high grafting density. The ligand-metal interaction can be switched between σ bonding and extended π backbonding by changing grafting conditions. The σ bonding of PEG-PA with NPs is strong and it can compete with other capping ligands including thiols, while the π backbonding is much weaker. The σ bonding is also demonstrated to improve the catalytic performance of Pd for ethanol oxidation and prevent surface absorption of the reaction intermediates. Those unique binding characteristics will enrich the toolbox in the control of colloidal surface chemistry and their applications using polymer ligands.

Number of sites-based solver for determining coverages from steady-state mean-field micro-kinetic models.

Kinetic models parameterized by ab-initio calculations have led to significant improvements in understanding chemical reactions in heterogeneous catalysis. These studies have been facilitated by implementations which determine steady-state coverages and rates of mean-field micro-kinetic models. As implemented in the open-source kinetic modeling program, CatMAP, the conventional solution strategy is to use a root-finding algorithm to determine the coverage of all intermediates through the steady-state expressions, constraining all coverages to be non-negative and to properly sum to unity. Though intuitive, this root-finding strategy causes issues with convergence to solution due to these imposed constraints. In this work, we avoid explicitly imposing these constraints, solving the mean-field steady-state micro-kinetic model in the space of number of sites instead of solving it in the space of coverages. We transform the constrained root-finding problem to an unconstrained least-squares minimization problem, leading to significantly improved convergence in solving micro-kinetic models and thus enabling the efficient study of more complex catalytic reactions.

Selective Deposition of N-Heterocyclic Carbene Monolayers on Designated Au Microelectrodes within an Electrode Array.

The incorporation of organic self-assembled monolayers (SAMs) in microelectronic devices requires precise spatial control over the self-assembly process. In this work, selective deposition of N-heterocyclic carbenes (NHCs) on specific electrodes within a two-microelectrode array is achieved by using pulsed electrodeposition. Spectroscopic analysis of the NHC-coated electrode arrays reveals that each electrode is selectively coated with a designated NHC. The impact of NHC monolayers on the electrodes' work function is quantified using Kelvin probe force microscopy. These measurements demonstrate that the work function values of each electrode can be independently tuned by the adsorption of a specific NHC. The presented deposition method enables to selectively coat designated microelectrodes in an electrode array with chosen NHC monolayers for tuning their chemical and electronic functionality.

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.

Ag20 Nanoclusters with Surface Azides as an Easily Functionalized Platform for Diverse Chemical Applications.

Modifying atomically precise nanocluster surfaces while maintaining the cluster core remains a key challenge. Herein, the synthesis, structure, and properties of two targeted Ag20 nanoclusters (NCs) with eight surface azide moieties, [CO3@Ag20(StBu)10(m-N3-C6H4COO)8(DMF)4] (1-m) and [CO3@Ag20(StBu)10(p-N3-C6H4COO)8(DMF)4] (1-p) are reported, where DMF is N,N-dimethylformamide. These AgNCs are designed to undergo cluster surface strain-promoted azide-alkyne cycloaddition (CS-SPAAC) reactions, introducing new functionality to the cluster surface. Reactivity is screened using model strained cyclooctynes. Reaction products and parent clusters are characterized by UV-vis, FT-IR, and NMR spectroscopies. The structure of the parent clusters and presence of surface azides is confirmed by single crystal X-ray diffraction (SCXRD) analysis. Clusters 1-m and 1-p are found to be amenable to CS-SPAAC reactions with retention of the NC frameworks, opening new routes for efficient modification of AgNC for applications.

Ligand-Directed Shape Reconfiguration in Inorganic Materials.

Polymer elastomers with reversible shape-changing capability have led to significant development of artificial muscles, functional devices, and soft robots. By contrast, reversible shape transformation of inorganic nanoparticles is notoriously challenging due to their relatively rigid lattice structure. Here, the authors demonstrate the synthesis of shape-changing nanoparticles via an asymmetrical surface functionalization process. Various ligands are investigated, revealing the essential role of steric hindrance from the functional groups. By controlling the unbalanced structural hindrance on the surface, the as-prepared clay nanoparticles can transform their shape in a fast, facile, and reversible manner. In addition, such flexible morphology-controlled mechanism provides a platform for developing self-propelled shape-shifting nanocollectors. Owing to the ion-exchanging capability of clay, these self-propelled nanoswimmers (NS) are able to autonomously adsorb rare earth elements with ultralow concentration, indicating the feasibility of using naturally occurring materials for self-powered nanomachine.

Ultrathin Flexible Silica Nanosheets with Surface Chemistry-Modulated Affinity to Mammalian Cells.

Flexibility of nanomaterials is challenging but worthy to tune for biomedical applications. Biocompatible silica nanomaterials are under extensive exploration but are rarely observed to exhibit flexibility despite the polymeric nature. Herein, a facile one-step route is reported to ultrathin flexible silica nanosheets (NSs), whose low thickness and high diameter-to-thickness ratio enables folding. Thickness and diameter can be readily tuned to enable controlled flexibility. Mechanism study reveals that beyond the commonly used surfactant, the "uncommon" one bearing two hydrophobic tails play a guiding role in producing sheeted/layered/shelled structures, while addition of ethanol appropriately relieved the strong interfacial tension of the assembled surfactants, which will otherwise produce large curled sheeted structures. With these ultrathin NSs, it is further shown that the cellular preference for particle shape and rigidity is highly dependent on surface chemistry of nanoparticles: under high particle-cell affinity, NSs, and especially the flexible ones will be preferred by mammalian cells for internalization or attachment, while this preference is basically invalid when the affinity is low. Therefore, properties of the ultrathin silica NSs can be effectively expanded and empowered by surface chemistry to realize improved bio-sensing or drug delivery.

Extremely Stable Ag-Based Photonics, Plasmonic, Optical, and Electronic Materials and Devices Designed with Surface Chemistry Engineering for Anti-Tarnish.

Silver (Ag) metal-based structures are promising building blocks for next-generation photonics and electronics owing to their unique characteristics, such as high reflectivity, surface plasmonic resonance effects, high electrical conductivity, and tunable electron transport mechanisms. However, Ag structures exhibit poor sustainability in terms of device performance because harsh chemicals, particularly S2- ions present in the air, can damage their structures, lowering their optical and electrical properties. Here, the surface chemistry of Ag structures with (3-mercaptopropyl)trimethoxysilane (MPTS) ligands at room temperature and under ambient conditions is engineered to prevent deterioration of their optical and electrical properties owing to S2- exposure. Regardless of the dimensions of the Ag structures, the MPTS ligands can be applied to each dimension (0D, 1D, and 3D). Consequently, highly sustainable plasmonic effects (Δλ < 2 nm), Fabry-Perot cavity resonance structures (Δλ < 2 nm), reflectors (ΔRReflectance < 0.5%), flexible electrodes (ΔRelectrical < 0.1 Ω), and strain gauge sensors (ΔGF < 1), even in S2- exposing conditions is achieved. This strategy is believed to significantly contribute to environmental pollution reduction by decreasing the volume of electronic waste.

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.

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.

Surface-Enhanced Raman Scattering Using 2D Materials.

The use of surface-enhanced Raman scattering (SERS) as a technique for detecting small amounts of (bio)chemical analytes has become increasingly popular in various fields. While gold and silver nanostructures have been extensively studied as SERS substrates, the availability of other types of substrates is currently expanding the applications of this spectroscopic method. Recently, researchers have begun exploring two-dimensional (2D) materials (e. g., graphene-like nanostructures) as substrates for SERS analysis. These materials offer unique optical properties, a well-defined structure, and the ability to modify their surface chemistry. As a contribution to advance this field, this concept article highlights the significance of understanding the chemical mechanism that underlies the experimental Raman spectra of chemisorbed molecules onto 2D materials' surfaces. Therefore, the article discusses recent advancements in fabricating substrates using 2D layered materials and the synergic effects of using their metallic composites for SERS applications. Additionally, it provides a new perspective on using Raman imaging in developing 2D materials as analytical platforms for Raman spectroscopy, an exciting emerging research area with significant potential.

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.

Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra.

The activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MOPs) impacts their performance in homogeneous catalysis. Specifically, through post-synthetic coordination of aliphatic imidazole ligands onto the exohedral Rh(II) axial sites of Rh-MOPs, we solubilized a cuboctahedral Rh-MOP in dichloromethane, thereby enabling its use as a homogeneous catalyst. We demonstrated that the presence of the coordinating ligand on the surface of the Rh-MOP does not hinder its catalytic activity in styrene aziridination and cyclopropanation reactions, thanks to the dynamic Rh-imidazole coordination bond. Finally, we used similar ligand exchange post-synthetic reactions to develop a ligand-mediated approach for precipitating the Rh-MOP catalyst, facilitating the recovery and reuse of Rh-MOPs as homogeneous catalysts.

Molybdenum(0)-Tricarbonyl Complex Supported by an Azacalix-pyridine Ligand: Synthesis, Characterization, Surface Deposition and Conversion to a Molybdenum(VI)-Trioxo Complex with O2.

Adsorption of metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans-effect" a dome-shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum-evaporable complex both activates CO and reacts with molecular oxygen (O2) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer. The molybdenum tricarbonyl- and trioxo complexes are investigated in the solid state, in homogeneous solution and on noble metal surfaces (Cu, Au) employing a range of spectroscopic and analytical methods.

A portable surface plasmon resonance (SPR) sensor for the detection of immunoglobulin A in plasma.

BACKGROUND: A life-threatening anaphylactic shock can occur if a patient with undiagnosed immunoglobulin A (IgA) deficiency (i.e., IgA levels <500 ng/mL) receives IgA-containing blood, hence the need for a rapid, point-of-care (POC) method for IgA deficiency screening. Enzyme-linked immunosorbent assay (ELISA) is routinely used to detect IgA, but this method requires trained specialists and ≥24 h to obtain a result. We developed a surface plasmon resonance (SPR)-based protocol to identify IgA-deficient patients or donors within 1 h. MATERIALS AND METHODS: The SPR sensor relies on the detection of IgAs captured by primary antibodies adsorbed on the SPR chip and quantified with secondary antibodies. The sensor was calibrated from 0 to 2000 ng/mL in buffer, IgA-depleted human serum, and plasma samples from IgA-deficient individuals. A critical concentration of 500 ng/mL was set for IgA deficiency. The optimized sensor was then tested on eight plasma samples with known IgA status (determined by ELISA), including five with IgA deficiency and three with normal IgA levels. RESULTS: The limit of detection was estimated at 30 ng/mL in buffer and 400 ng/mL in diluted plasma. The results obtained fully agreed with ELISA among the eight plasma samples tested. The protocol distinguished IgA-deficient from normal samples, even for samples with an IgA concentration closer to critical concentration. DISCUSSION: In conclusion, we developed a reliable POC assay for the quantification of IgA in plasma. This test may permit POC testing at blood drives and centralized centers to maintain reserves of IgA-deficient blood and in-hospital testing of blood recipients.

The Entropy of van der Waals Fluid.

Thermodynamic state functions are fundamental quantities in many fields. In this work, the van der Waals (vdW) equation of state and calculation formulas of state functions are derived with statistical thermodynamic method in three-dimensional (3D) and two-dimensional (2D) spaces. The heat capacity at constant volume (CV,m ) or area (CA,m ) is exactly the same as that of ideal gas, but the heat capacity at constant pressure (Cp,m ) and other state functions are different from those of ideal gas. The vdW equation of state is a cubic equation, which leads to the fact that the entropy and free energy changes of vdW fluid can be expressed as explicit expressions of volume rather than pressure. Therefore, the adsorbate entropy at constant area can still be theoretically proven to have a linear relationship with the gas-phase entropy at constant volume. However, the linear correlation between it and gas-phase entropy at constant pressure is no longer strictly true in theory. In addition, since the vdW equation of state is applicable to both gas and liquid, the linear correlation between adsorbate entropy and liquid-phase entropy can also be found. At last, the reference state for real gas or fluid at a constant molar volume is suggested.