Insights into the Mechanism of Protein Loading by Chain-Length Asymmetric Complex Coacervates.

The study of the phase behavior of polyelectrolyte complex coacervates has attracted significant attention in recent years due to their potential use as membrane-less organelles, microreactors, and drug delivery platforms. In this work, we investigate the mechanism of protein loading in chain-length asymmetric complex coacervates composed of a polyelectrolyte and an oppositely charged multivalent ion. Unlike the symmetric case (polycation + polyanion), we show that protein loading is highly selective based on the protein's net charge: only proteins with charges opposite to the polyelectrolyte can be loaded.

Harnessing concerted functions in confined environments: cascading enzymatic reactions in nanofluidic biosensors for sensitive detection of arginine.

We developed an arginine-responsive biosensor by integrating cascade enzymatic reactions into nanochannels functionalized with weak polyelectrolytes, which serve as "reactive signal amplifiers." This approach enhances device performance and broadens the detectable analyte range by generating high local analyte concentrations. The nanofluidic biosensor operates rapidly (<5 minutes) with a low detection limit of 3 μM.

Sensing creatinine in urine via the iontronic response of enzymatic single solid-state nanochannels.

In this study, we investigate the integration of the enzyme creatinine deiminase into solid-state nanopore walls through electrostatic assembly for the development of creatinine sensors. In these asymmetric single nanochannels, ionic transport is determined by the surface charge inside the channel, resulting in diode-like behavior that rectifies ionic current. The efficiency of such rectification depends on the surface charge density.

Unlocking Nanoprecipitation: A Pathway to High Reversibility in Nanofluidic Memristors.

Solid-state nanochannels have emerged as a promising platform for the development of ionic circuit components with analog properties to their traditional electronic counterparts. In the last years, nanofluidic devices with memristive properties have attracted special interest due to their applicability in, for example, the construction of brain-like computing systems. In this work, an asymmetric track-etched nanofluidic channel with memory-enhanced ion transport is reported.

Digitalization of Enzyme-Linked Immunosorbent Assay with Graphene Field-Effect Transistors (G-ELISA) for Portable Ferritin Determination.

Herein, we present a novel approach to quantify ferritin based on the integration of an Enzyme-Linked Immunosorbent Assay (ELISA) protocol on a Graphene Field-Effect Transistor (gFET) for bioelectronic immunosensing. The G-ELISA strategy takes advantage of the gFET inherent capability of detecting pH changes for the amplification of ferritin detection using urease as a reporter enzyme, which catalyzes the hydrolysis of urea generating a local pH increment. A portable field-effect transistor reader and electrolyte-gated gFET arrangement are employed, enabling their operation in aqueous conditions at low potentials, which is crucial for effective biological sample detection.

Manipulating Ion Transport Regimes in Nanomembranes via a "Pore-in-Pore" Approach Enabled by the Synergy of Metal-Organic Frameworks and Solid-State Nanochannels.

Solid-state nanochannels (SSNs) have emerged as promising platforms for controlling ionic transport at the nanoscale. SSNs are highly versatile, and this feature can be enhanced through their combination with porous materials such as Metal-Organic Frameworks (MOF). By selection of specific building blocks and experimental conditions, different MOF architectures can be obtained, and this can influence the ionic transport properties through the nanochannel.

Unified Roadmap for ZIF-8 Nucleation and Growth: Machine Learning Analysis of Synthetic Variables and Their Impact on Particle Size and Morphology.

Metal-organic frameworks (MOFs) have settled in the scientific community over the last decades as versatile materials with several applications. Among those, zeolitic imidazolate framework 8 (ZIF-8) is a well-known MOF that has been applied in various and diverse fields, from drug-delivery platforms to microelectronics. However, the complex role played by the reaction parameters in controlling the size and morphology of ZIF-8 particles is still not fully understood.

Insight into the transport of ions from salts of moderated solubility through nanochannels: negative incremental resistance assisted by geometry.

In this study, the transport of salt with moderate solubility through bioinspired solid-state nanochannels was comprehensively investigated. For this purpose, bullet-shaped channels were fabricated and exposed to KClO, a monovalent salt with moderate solubility. These channels displayed the typical rectifying behavior characteristic of asymmetrical channels but with one remarkable difference, the iontronic output exhibited a negative incremental resistance phenomenon of high gating efficiency when the transmembrane voltage in the open state was increased enough, giving rise to an inactivated state characterized by a low and stable ion current.

Noninvasive and Multiplex Self-Test of Kidney Disease Biomarkers with Graphene-Based Lab-on-a-Chip (G-LOC): Toward Digital Diagnostics in the Hands of Patients.

Chronic kidney disease is one of the major health issues worldwide. However, diagnosis is now highly centralized in large laboratories, resulting in low access to patient monitoring and poor personalized treatments. This work reports the development of a graphene-based lab-on-a-chip (G-LOC) for the digital testing of renal function biomarkers in serum and saliva samples.

Nanoprecipitation-Enhanced Sensitivity in Enzymatic Nanofluidic Biosensors.

Single nanochannels show unique transport properties due to nanoconfinement. It has been demonstrated that at submillimolar concentrations of divalent cations, a nanoprecipitation reaction can occur in nanochannels. Although several reports have shown, described, and modeled the nanoprecipitation process, no further advantages have been taken from this phenomenon.

Advances in nanofluidic field-effect transistors: external voltage-controlled solid-state nanochannels for stimulus-responsive ion transport and beyond.

Ion channels, intricate protein structures facilitating precise ion passage across cell membranes, are pivotal for vital cellular functions. Inspired by the remarkable capabilities of biological ion channels, the scientific community has ventured into replicating these principles in fully abiotic solid-state nanochannels (SSNs). Since the gating mechanisms of SSNs rely on variations in the physicochemical properties of the channel surface, the modification of their internal architecture and chemistry constitutes a powerful strategy to control the transport properties and, consequently, render specific functionalities.

Poly(allylamine)-tripolyphosphate Ionic Assemblies as Nanocarriers: Friend or Foe?

Designing effective drug nanocarriers that are easy to synthesize, robust, and nontoxic is a significant challenge in nanomedicine. Polyamine-multivalent molecule nanocomplexes are promising drug carriers due to their simple and all-aqueous manufacturing process. However, these systems can present issues of colloidal instability over time and cellular toxicity due to the cationic polymer.

Transduction of Amine-Phosphate Supramolecular Interactions and Biosensing of Acetylcholine through PEDOT-Polyamine Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are important devices for the development of flexible and wearable sensors due to their flexibility, low power consumption, sensitivity, selectivity, ease of fabrication, and compatibility with other flexible materials. These features enable the creation of comfortable, versatile, and efficient portable devices that can monitor and detect a wide range of parameters for various applications. Herein, we present OECTs based on PEDOT-polyamine thin films for the selective monitoring of phosphate-containing compounds.

Phase Behavior and Electrochemical Properties of Highly Asymmetric Redox Coacervates.

This work reports the phase behavior and electrochemical properties of liquid coacervates made of ferricyanide and poly(ethylenimine). In contrast to the typical polyanion/polycation pairs used in liquid coacervates, the ferricyanide/poly(ethylenimine) system is highly asymmetric because poly(ethylenimine) has approximately 170 charges per molecule, while ferricyanide has only 3. Two types of phase diagrams were measured and fitted with a theoretical model.

Field-effect transistors engineered via solution-based layer-by-layer nanoarchitectonics.

The layer-by-layer (LbL) technique has been proven to be one of the most versatile approaches in order to fabricate functional nanofilms. The use of simple and inexpensive procedures as well as the possibility to incorporate a very wide range of materials through different interactions have driven its application in a wide range of fields. On the other hand, field-effect transistors (FETs) are certainly among the most important elements in electronics.

PEDOT-Polyamine-Based Organic Electrochemical Transistors for Monitoring Protein Binding.

The fabrication of efficient organic electrochemical transistors (OECTs)-based biosensors requires the design of biocompatible interfaces for the immobilization of biorecognition elements, as well as the development of robust channel materials to enable the transduction of the biochemical event into a reliable electrical signal. In this work, PEDOT-polyamine blends are shown as versatile organic films that can act as both highly conducting channels of the transistors and non-denaturing platforms for the construction of the biomolecular architectures that operate as sensing surfaces. To achieve this goal, we synthesized and characterized films of PEDOT and polyallylamine hydrochloride (PAH) and employed them as conducting channels in the construction of OECTs.

Polyelectrolyte-multivalent molecule complexes: physicochemical properties and applications.

The complexation of polyelectrolytes with other oppositely charged structures gives rise to a great variety of functional materials with potential applications in a wide spectrum of technological fields. Depending on the assembly conditions, polyelectrolyte complexes can acquire different macroscopic configurations such as dense precipitates, nanosized colloids and liquid coacervates. In the past 50 years, much progress has been achieved to understand the principles behind the phase separation induced by the interaction of two oppositely charged polyelectrolytes in aqueous solutions, especially for symmetric systems (systems in which both polyions have similar molecular weight and concentration).

Interface Engineering of "Clickable" Organic Electrochemical Transistors toward Biosensing Devices.

"Clickable" organic electrochemical transistors (OECTs) allow the reliable and straightforward functionalization of electronic devices through the well-known click chemistry toolbox. In this work, we study various aspects of the click chemistry-based interface engineering of "clickable" OECTs. First, different channel architectures are investigated, showing that PEDOT-N films can properly work as a channel of the transistors.

Electrochemically addressed FET-like nanofluidic channels with dynamic ion-transport regimes.

Nanofluidic channels in which the ionic transport can be modulated by the application of an external voltage to the nanochannel walls have been described as nanofluidic field effect transistors (nFETs) because of their analogy with electrolyte-gated field effect transistors. The creation of nFETs is attracting increasing attention due to the possibility of controlling ion transport by using an external voltage as a non-invasive stimulus. In this work, we show that it is possible to extend the actuation range of nFETs by using the supporting electrolyte as a "chemical effector".

"Clickable" Organic Electrochemical Transistors.

Interfacing the surface of an organic semiconductor with biological elements is a central quest when it comes to the development of efficient organic bioelectronic devices. Here, we present the first example of "clickable" organic electrochemical transistors (OECTs). The synthesis and characterization of an azide-derivatized EDOT monomer (azidomethyl-EDOT, EDOT-N) are reported, as well as its deposition on Au-interdigitated electrodes through electropolymerization to yield PEDOT-N-OECTs.

Species Distribution in Bicontinuous Phase Systems for Enhanced Oil Recovery Probed by Single-Sided NMR.

Multiphase aqueous-organic systems where a bicontinuous phase is in equilibrium with an excess organic and aqueous phase find various applications in industry. These systems─also known as Winsor III─are complex not only for the different phases that develop therein but also because they are multicomponent systems. In this work, we explore for the first time the use of a benchtop low-field single-sided NMR to determine the species distribution in Winsor III systems.

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).

Switchable Ion Current Saturation Regimes Enabled via Heterostructured Nanofluidic Devices Based on Metal-Organic Frameworks.

The use of track-etched membranes allows further fine-tuning of transport regimes and thus enables their use in (bio)sensing and energy-harvesting applications, among others. Recently, metal-organic frameworks (MOFs) have been combined with such membranes to further increase their potential. Herein, the creation of a single track-etched nanochannel modified with the UiO-66 MOF is proposed.