Ion-Fluid Transport-Control Feedback along Nanopore Networks.

Biological signaling correlates with the interrelation between ion and nanofluidic transportation pathways. However, artificial embodies with reconfigurable ion-fluid transport interaction aspects remain largely elusive. Herein, we unveiled an intimate interplay between nanopore-driven advancing flow and ion carriage for the spontaneous imbibition of aqueous solutions at the nanoporous thin film level. Ionic factors dominate transport phenomena processing and integration (ions influence fluid motion, which in turn governs the self-regulated ion traveling). We show an ion-induced translation effect that finely converts a chemical input, the nature of ions, into a related fluidic output: modulation of the extent of imbibition. We further find complex imbibition dynamics induced by the ion type and population. We peculiarly pinpoint a stop-and-go effective transport process with a programmable delay time triggered by selective guest-host interactions. The ion-fluid transport interplay is captured by a simple model that considers the counterbalance between the capillary infiltration and solution concentration, owing to water loss at the nanoporous film-air interface. Our results demonstrate that nanopore networks present fresh scenarios for understanding and controlling autonomous macroscopic liquid locomotion and offer a distinctive working principle for smart ion operation.

Fe-Ni porphyrin/mesoporous titania thin film electrodes: a bioinspired nanoarchitecture for photoelectrocatalysis.

Porphyrin and porphyrinoid derivatives have been extensively studied in the assembly of catalysts and sensors, seeking biomimetic and bioinspired activity. In particular, Fe and Ni porphyrins can be used for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by immobilization of these molecular catalysts on semiconductor materials. In this study, we designed a hybrid material containing a crystalline mesoporous TiO2 thin film in which the catalytic centres are Ni-porphyrin (NiP), Fe-porphyrin (FeP), and a NiP/FeP bimetallic system to assess whether the coexistence of both metalloporphyrins improves the OER activity. The obtained photoelectrodes were physicochemically and morphologically characterized through high-resolution FE-SEM images, UV-vis and Raman spectroscopies, cyclic voltammetry, and impedance measurements. The results show a differential behavior of the mono- and bimetallic porphyrin systems, where the Fe(iii) centre in FeP may increase the acidity and lower the reduction potential of the Ni2+/3+ couple when co-deposited with NiP leading to an improved photoelectrochemical water-oxidation performance. We have validated the cooperative effect of both metal complexes within this novel system, where the µ-peroxo-bridged interaction between Fe and Ni is integrated into a supramolecular heterometallic structure of porphyrins.

Enhancement of electrocatalysis through magnetic field effects on mass transport.

Magnetic field effects on electrocatalysis have recently gained attention due to the substantial enhancement of the oxygen evolution reaction (OER) on ferromagnetic catalysts. When detecting an enhanced catalytic activity, the effect of magnetic fields on mass transport must be assessed. In this study, we employ a specifically designed magneto-electrochemical system and non-magnetic electrodes to quantify magnetic field effects. Our findings reveal a marginal enhancement in reactions with high reactant availability, such as the OER, whereas substantial boosts exceeding 50% are observed in diffusion limited reactions, exemplified by the oxygen reduction reaction (ORR). Direct visualization and quantification of the whirling motion of ions under a magnetic field underscore the importance of Lorentz forces acting on the electrolyte ions, and demonstrate that bubbles' movement is a secondary phenomenon. Our results advance the fundamental understanding of magnetic fields in electrocatalysis and unveil new prospects for developing more efficient and sustainable energy conversion technologies.

Hybrid mesoporous electrodes evidence CISS effect on water oxidation.

Controlling product selectivity is essential for improving the efficiency of multi-product reactions. Electrochemical water oxidation is a reaction of main importance in different applications, e.g., renewable energy schemes and environmental protection, where H2O2 and O2 are the two principal products. In this Communication, the product selectivity of electrochemical water oxidation was controlled by making use of the chiral induced spin selectivity (CISS) effect at mesoporous-TiO2 on the molecule-modified Au substrate. Our results show a decrease in H2O2 formation when using chiral hetero-helicene molecules adsorbed on the Au substrate. We propose a mechanism for this kinetic effect based on the onset of CISS-induced spin polarization on the Au-helicene chiral interface. We also present a new tunable substrate to investigate the CISS mechanism.

Advances in Nanomaterials and Composites Based on Mesoporous Materials as Antimicrobial Agents: Relevant Applications in Human Health.

Nanotechnology has emerged as a cornerstone in contemporary research, marked by the advent of advanced technologies aimed at nanoengineering materials with diverse applications, particularly to address challenges in human health. Among these challenges, antimicrobial resistance (AMR) has risen as a significant and pressing threat to public health, creating obstacles in preventing and treating persistent diseases. Despite efforts in recent decades to combat AMR, global trends indicate an ongoing and concerning increase in AMR. The primary contributors to the escalation of AMR are the misuse and overuse of various antimicrobial agents in healthcare settings. This has led to severe consequences not only in terms of compromised treatment outcomes but also in terms of substantial financial burdens. The economic impact of AMR is reflected in skyrocketing healthcare costs attributed to heightened hospital admissions and increased drug usage. To address this critical issue, it is imperative to implement effective strategies for antimicrobial therapies. This comprehensive review will explore the latest scientific breakthroughs within the metal-organic frameworks and the use of mesoporous metallic oxide derivates as antimicrobial agents. We will explore their biomedical applications in human health, shedding light on promising avenues for combating AMR. Finally, we will conclude the current state of research and offer perspectives on the future development of these nanomaterials in the ongoing battle against AMR.

Sunlight-Driven Photocatalysis for a Set of 3D Metal-Porphyrin Frameworks Based on a Planar Tetracarboxylic Ligand and Lanthanide Ions.

Metal-porphyrin frameworks (MPFs) with trivalent lanthanide ions are the most sought-after materials in the past decade. Their porosities are usually complemented by optical properties imparted by the metal nodes, making them attractive multifunctional materials. Here, we report a novel family of 3D MPFs obtained through solvothermal reactions between tetrakis(4-carboxyphenyl) porphyrin (H4TCPP) and different lanthanide sources, yielding an isostructural family of compounds along the lanthanide series: [Ln2(DMF)(TCPP)1.5] for Ln = La, Ce, Nd, Pr, Er, Y, Tb, Dy, Sm, Eu, Gd, and Tm. Photoluminescent properties of selected phases were explored at room temperature. Also, the photocatalytic performance exhibited by these compounds under sunlight exposure is promising for its implementation in organic pollutant degradation. In order to study the photocatalytic activity of Ln-TCPPs in an aqueous medium, methylene blue (MB) was used as a contaminant model. The efficiency for MB degradation was Sm > Y > Yb > Gd > Er > Eu > either no catalyst or no light, obtaining more than 70% degradation at 120 min with Sm-TCPP. These results open the possibility of using these compounds in optical and optoelectronic devices for water remediation and sensing.

Ordered Mesoporous Electrodes for Sensing Applications.

Electrochemical sensors have become increasingly relevant in fields such as medicine, environmental monitoring, and industrial process control. Selectivity, specificity, sensitivity, signal reproducibility, and robustness are among the most important challenges for their development, especially when the target compound is present in low concentrations or in complex analytical matrices. In this context, electrode modification with Mesoporous Thin Films (MTFs) has aroused great interest in the past years. MTFs present high surface area, uniform pore distribution, and tunable pore size. Furthermore, they offer a wide variety of electrochemical signal modulation possibilities through molecular sieving, electrostatic or steric exclusion, and preconcentration effects which are due to mesopore confinement and surface functionalization. In order to fully exploit these advantages, it is central to develop reproducible routes for sensitive, selective, and robust MTF-modified electrodes. In addition, it is necessary to understand the complex mass and charge transport processes that take place through the film (particularly in the mesopores, pore surfaces, and interfaces) and on the electrode in order to design future intelligent and adaptive sensors. We present here an overview of MTFs applied to electrochemical sensing, in which we address their fabrication methods and the transport processes that are critical to the electrode response. We also summarize the current applications in biosensing and electroanalysis, as well as the challenges and opportunities brought by integrating MTF synthesis with electrode microfabrication, which is critical when moving from laboratory work to in situ sensing in the field of interest.

A Comparative Study of PMETAC-Modified Mesoporous Silica and Titania Thin Films for Molecular Transport Manipulation.

The manipulation and understanding of molecular transport across functionalized nanopores will take us closer to mimicking biological membranes and thus to design high-performance permselective separation systems. In this work, Surface-initiated atom transfer radical polymerization (SI-ATRP) of (2-methacryloyloxy)-ethyltrimethylammonium chloride (METAC) was performed on both mesoporous silica and mesoporous titania thin films. Pores were proven to be filled using ellipsometry and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Furthermore, the employed method leads to a polymer overlayer, whose thickness could be discriminated using a double-layer ellipsometry model. Cyclic voltammetry experiments reveal that the transport of electrochemically active probes is affected by the PMETAC presence, both due to the polymer overlayer and the confined charge of the pore-tethered PMETAC. A more detailed study demonstrates that ion permeability depends on the combined role of the inorganic scaffolds' (titania and silica) surface chemistry and the steric and charge exclusion properties of the polyelectrolyte. Interestingly, highly charged negative walls with positively charged polymers may resemble zwitterionic polymer behavior in confined environments.

Impact of PEGylation on the degradation and pore organization in mesoporous silica nanoparticles: A study of the inner mesoporous structure in physiologically relevant ionic conditions.

The degradation of mesoporous silica nanoparticles (MSNs) in the biological milieu due to silica hydrolysis plays a fundamental role for the delivery of encapsulated drugs and therapeutics. However, little is known on the evolution of the pore arrangement in the MSNs in biologically relevant conditions. Small Angle X-ray scattering (SAXS) studies were performed on unmodified and PEGylated MSNs with a MCM-48 pore structure and average sizes of 140 nm, exposed to simulated body fluid solution (SBF) at pH 7.4 for different time intervals from 30 min to 24 h. Experiments were performed with silica concentrations below, at and over 0.14 mg/mL, the saturation concentration of silica in water at physiological temperature. At silica concentrations of 1 mg/mL (oversaturation), unmodified MSNs show variation in interpore distances over 6 h exposure to SBF, remaining constant thereafter. A decrease in radius of gyration is observed over the same time. Mesoporosity and radius of gyration of unmodified MSNs remain then unchanged up to 24 h. PEGylated MSNs at 1 mg/mL concentration show a broader diffraction peak but no change in the position of the peak is observed following 24 h exposure to SBF. PEGylated MSNs at 0.01 mg/mL show no diffraction peaks already after 30 min exposure to SBF, while at 0.14 mg/mL a small diffraction peak is present after 30 min exposure but disappears after 1 h.

Core vs. surface labelling of mesoporous silica nanoparticles: advancing the understanding of nanoparticle fate and design of labelling strategies.

Despite great interest in the use of silica mesoporous nanoparticles (MSNs) in drug delivery little is known on their biological fate. Positron emission tomography (PET) studies of radiolabelled MSNs face a major difficulty due to the degradation of the MSNs during circulation as it is difficult to assign activity values to either the MSNs or their degradation products. Here, a PET study is conducted using two strategies of labelling. MSNs are either radiolabelled in the core by complexation with silanols from the MSNs with 89Zr, or on the MSN coating through attachment of 131I radiolabelled Lin-TT1 (AKRGARSTA), a homing peptide for targeting cancer tissue. Results from the biodistribution of MSNs with the two labels are compared, obtaining meanful information on the fate of MSNs. While MSNs accumulate in liver and spleen, MSN degradation products 89Zr or silicate bearing the radioisotope, are found in the bones and probably in lungs. A partial detachment of the peptide from the surface of the MSN is also observed. This work highlights the importance of choosing an appropriate labelling strategy for nanoparticles since core or surface labelling may result in different particle biodistribution if the labelled component degrades or the label detaches.

Droplets in underlying chemical communication recreate cell interaction behaviors.

The sensory-motor interaction is a hallmark of living systems. However, developing inanimate systems with "recognize and attack" abilities remains challenging. On the other hand, controlling the inter-droplet dynamics on surfaces is key in microengineering and biomedical applications. We show here that a pair of droplets can become intelligently interactive (chemospecific stimulus-response inter-droplet autonomous operation) when placed on a nanoporous thin film surface. We find an attacker-victim-like non-reciprocal interaction between spatially separated droplets leading to an only-in-one shape instability that triggers a drop projection to selectively couple, resembling cellular phenomenologies such as pseudopod emission and phagocytic-like functions. The nanopore-driven underlying communication and associated chemical activity are the main physical ingredients behind the observed behavior. Our results reveal that basic features found in many living cell types can emerge from a simple two-droplet framework. This work is a promising step towards the design of microfluidic smart robotics and for origin-of-life protocell models.

Importance of the Structural and Physicochemical Properties of Silica Nanoshells in the Photothermal Effect of Silica-Coated Au Nanoparticles Suspensions.

In this work, monodisperse silica-coated gold nanoparticles (NPs) were synthesized and used for obtaining aqueous colloidal dispersions with an optimum relationship between colloidal stability and photothermal activity. The idea behind this design was to produce systems with the advantages of the presence of a silica shell (biocompatibility, potential for surface modification, and protecting effect) with a minimal loss of optical and thermal properties. With this aim, the photothermal properties of NPs with silica shells of different thicknesses were analyzed under conditions of high radiation extinction. By using amorphous, gel-like silica coatings, thicknesses higher than 40 nm could be obtained without an important loss of the light absorption capacity of the colloids and with a significant photothermal response even at low NP concentrations. The effects produced by changes in the solvent and in the NP concentration were also analyzed. The results show that the characteristics of the shell control both, the photothermal effect and the optical properties of the colloidal dispersions. As the presence of a silica shell strongly enhances the possibilities of adding cargo molecules or probes, these colloids can be considered of high interest for biomedical therapies, sensing applications, remote actuation, and other technological applications.

In Vivo Tracking of the Degradation of Mesoporous Silica through 89 Zr Radio-Labeled Core-Shell Nanoparticles.

While mesoporous silica nanoparticles (MSNs) are extensively studied as high-potential drug delivery platforms, the successful clinical translation of these nanocarriers strongly depends on their biodistribution, biodegradation, and elimination patterns in vivo. Here, a novel method is reported to follow the in vivo degradation of MSNs by tracking a radioactive label embedded in the silica structure. Core-shell silica nanoparticles (NPs) with a dense core and a mesoporous shell are labeled with low quantities of the positron emitter 89 Zr, either in the dense core or in the mesoporous shell. In vivo positron emission tomography imaging and ex vivo organ measurements reveal a remarkable difference in the 89 Zr biodistribution between the shell-labeled and the core-labeled NPs. Release of the radiotracer from shell-labeled NPs is used as a probe of the extent of silica dissolution, and a prompt release of the radioisotope is observed, with partial excretion already in the first 2 h post injection, and a slower accumulation in bones over time. On the other hand, when 89 Zr is embedded in the nanoparticle core, the biodistribution remains largely unchanged during the first 6 h. These findings indicate that MSNs have fast, hour-scale, degradation kinetics in vivo.

Determination of Antibacterial Activity of Film Coatings Against Four Clinically Relevant Bacterial Strains.

Antibacterial coatings have currently gained great importance in biomedical technology investigations. Because of the spatial arrangement of the film coatings, evaluation of antibacterial activity presents a new challenge regarding traditional bacterial counting methods. In this protocol, four clinically relevant pathogens, Salmonella typhimurium, Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus were incubated on titania mesostructured thin film coatings for 24 h. Then, cell viability was studied considering three methods: counting of the number of colony forming units (CFU), live/dead staining, and quantification of extracellular DNA in suspension. Firstly, bacterial count was determined by the standard plate-count technique. Secondly, bacteria membrane integrity was evaluated by utilization of two fluorescent dyes, which allow distinction between live (membrane intact) and dead (membrane disrupted) bacteria. Lastly, extracellular DNA was quantified by spectrophotometry. In this manner, the three aforementioned techniques enabled the study of bacterial viability by qualitative and quantitative analyses.

Nanopore-Mediated Spontaneous Dilution of Droplets: When Evaporation Turns to a Dilutor.

Droplet evaporation on surfaces is ubiquitous and affects areas as diverse as climate, microbiology, the chemical industry, and materials science. While solute concentration is the universally taken-for-granted behavior in drop evaporation, the present work shows that saline droplets evaporating on nanoporous thin-film surfaces can get diluted rather than concentrated. The driving mechanism of this phenomenon is attributed to the flow drawn from the drop through the nanopores by an annular peripheral evaporation. This fluid transport can continuously collect the salt solution from a concentrated region of the droplet, which is induced by radial microflows during drop evaporation. The coupling of these processes leads to the overall drop dilution effect. The influence of substrate temperature and drop volume was also investigated. This study opens up new perspectives on many natural phenomena and offers alternatives for physicochemical applications in small dimensions as well as for water desalination technologies.

Introduction to celebrating Latin American talent in chemistry.

In celebration of the excellence and breadth of Latin American research achievements across the chemical sciences, we are delighted to present an introduction to the themed collection, Celebrating Latin American talent in chemistry.

Zinc porphyrin/mesoporous titania thin film electrodes: a hybrid material nanoarchitecture for photocatalytic reduction.

In this work, photocatalytic reduction of methyl viologen is achieved using zinc tetra(4-N-methylpyridyl)porphine (ZnP) functionalized mesoporous titania thin films (MTTF). Metalloporphyrins are the core of natural systems that harvest energy from the sun. Thus, a bioinspired approach is used, taking advantage of ZnP sensitizing capabilities and MTTF organized structure.

E-waste upcycling for the synthesis of plasmonic responsive gold nanoparticles.

One of the current challenges in circular economy is the ability to transform waste into valuable products. In this work, waste of electrical and electronic equipment (WEEE) was used as a gold source to prepare stable gold nanoparticles (AuNP). The proposed methodology involves a series of physical and chemical separation steps, carefully designed according to the complex nature of the selected WEEE and the targeted product. In a first step, pins from microprocessors were separated by mechanical treatments, allowing to concentrate gold in a metallic fraction. A two-step hydrometallurgical method was subsequently performed, to obtain a Au (III) enriched solution. Such solution was used as a secondary raw material to obtain AuNP. For that purpose, a specific synthetic method was developed, adapted to the high acidity and ionic strength of the solution. Thanks to the use of two easily available reducing agents (sodium citrate and ascorbic acid) and a polymeric stabilizer (PVP), it was possible to obtain high purity AuNP presenting a mixture of well-defined spherical and triangular shapes. These AuNP were finally deposited onto glass substrates and present a sensitive response to refractive index changes in the environment, a necessary condition towards application in optical sensors. In summary, this upcycling case study demonstrates that e-waste can successfully replace primary raw materials to obtain highly valuable and useful nanomaterials. These results highlight the potential of urban mining as a sustainable and circular approach to the development of nanotechnologies.

BSA-capped gold nanoclusters as potential theragnostic for skin diseases: Photoactivation, skin penetration, in vitro, and in vivo toxicity.

BSA-capped gold nanoclusters are promising theragnostic systems that can be excited to render both fluorescence emission and reactive oxygen species. Although their synthesis and photoluminescence properties are already well described, more accurate information about their use as photosensitizers is required in order to advance towards health applications. In this work, we have obtained BSA-capped gold nanoclusters and characterized their photophysics by different techniques. Singlet oxygen production was detected upon irradiation, which was enough to produce toxicity on two cell lines. Remarkably, an internal energy transfer, probably due to the presence of smaller nanoclusters and the contribution of oxidized residues of BSA in the system, caused fluorescence emission near 640 nm after excitation in the UV range. Additionally, the system was capable of penetrating human skin beyond the stratum corneum, which enhances the potential of these nanoclusters as bifunctional photodynamic therapy effectors and biomarkers with application in a diversity of skin diseases. In the absence of radiation, BSA-capped gold nanoclusters did not cause toxicity in vitro, while their toxic effect on an in vivo model as zebrafish was determined.