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Molecularly imprinted silica nanoparticles (SP-MIP) are synthesized for the real-time optical detection of low-molecular-weight compounds. Azo-initiator-modified silica beads are functionalized through reversible addition-fragmentation chain transfer (RAFT) polymerization, which leads to efficient control of the grafted layer. The copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDMA) on azo initiator-coated silica particles (≈100 nm) using chain transfer agent (2-phenylprop-2-yl-dithiobenzoate) is carried out in the presence of a target analyte molecule (l-Boc-phenylalanine anilide, l-BFA). The chemical and morphological properties of SP-MIP are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface analysis, and thermogravimetric analysis. Finally, SP-MIP is located on the gold surface to be used as a biorecognition layer on the surface plasmon resonance spectrometer (SPR). The sensitivity, response time, and selectivity of SP-MIP are investigated by three similar analogous molecules (l-Boc-Tryptophan, l-Boc-Tyrosine, and l-Boc-Phenylalanine) and the imprinted particle surface showed excellent relative selectivity toward l-Boc-Phenylalanine (l-BFA) (k = 61), while the sensitivity is recorded as limit of detection = 1.72 × 10-4 m.
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Delivery systems that can encapsulate a precise amount of drug and offer a spatiotemporally controlled drug release are being actively sought for safe yet effective cancer therapy. Compared to polymer nanoparticle (NP)-based delivery systems that rely on physical drug encapsulation, NPs derived from stimuli-sensitive covalent polymer-drug conjugates (PDCs) have emerged as promising alternatives offering precise control over drug dosage and spatiotemporal drug release. Herein, we report a reduction-sensitive PDC "Dex-SS-PTXL" synthesized by conjugating dextran and paclitaxel (PTXL) through a disulfide bond-bearing linker. The synthesized Dex-SS-PTXL PDC with a precise degree of substitution in terms of the percentage of repeat units of dextran covalently conjugated to PTXL (27 ± 0.6%) and the amount of drug carried by the PDC (39 ± 1.4 wt %) was found to self-assemble into spherical NPs with an average size of 110 ± 34 nm and a ζ-potential of -14.09 ± 8 mV. The reduction-sensitive Dex-SS-PTXL NPs were found to release PTXL exclusively in response to the reducing agent concentration reflective of the intracellular reducing environment of the tumor cells. Challenging BT-549 and MCF-7 cells with Dex-SS-PTXL NPs revealed significant cytotoxicity, while the IC50 values and the mode of action (mitotic arrest) of Dex-SS-PTXL NPs were found to be comparable to those of free PTXL, highlighting the active nature of the intracellularly released drug. The developed PDC with its unique ability to self-assemble into NPs and stimuli-responsive drug release can enhance the success of the NP-based drug delivery systems during clinical translation.
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PaclitaxelRESUMEN
Functionalization of metal-organic frameworks (MOFs) is critical in exploring their structural and chemical diversity for numerous potential applications. Herein, we report multiple approaches for the tandem postsynthetic modification (PSM) of various MOFs derived from Zr(IV), Al(III), and Zn(II). Our current work is based on our efforts to develop a wide range of MOF platforms with a dynamic functional nature that can be chemically switched via thermally triggered reversible Diels-Alder (DA) and hetero-Diels-Alder (HDA) ligations. Furan-tagged MOFs (furan-UiO-66-Zr) were conjugated with maleimide groups bearing dienophiles to prepare MOFs with a chemically switchable nature. As HDA pairs, phosphoryl dithioester-based moieties and cyclopentadiene (Cp)-grafted MOF (Cp-MIL-53-Al) were utilized to demonstrate the cleavage and rebonding of the linkages as a function of temperature. In addition to these strategies, the Michael addition reaction was also applied for the tandem PSM of IRMOF-3-Zn. Maleimide groups were postsynthetically introduced in the MOF lattice, which were further ligated with cysteine-based biomolecules via the thiol-maleimide Michael addition reaction. On the basis of the versatility of the herein presented chemistry, we expect that these approaches will help in designing a variety of sophisticated functional MOF materials addressing diverse applications.
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Spectroscopy with planar optical waveguides is still an active field of research for the quantitative analysis of various supramolecular surface architectures and processes, and for applications in integrated optical chip communication, direct chemical sensing, etc. In this contribution, we summarize some recent development in optical waveguide spectroscopy using nanoporous thin films as the planar substrates that can guide the light just as well as bulk thin films. This is because the nanoporosity is at a spacial length-scale that is far below the wavelength of the guided light; hence, it does not lead to an enhanced scattering or additional losses of the optical guided modes. The pores have mainly two effects: they generate an enormous inner surface (up to a factor of 100 higher than the mere geometric dimensions of the planar substrate) and they allow for the exchange of material and charges between the two sides of the solid thin film. We demonstrate this for several different scenarios including anodized aluminum oxide layers for the ultrasensitive determination of the refractive index of fluids, or the label-free detection of small analytes binding from the pore inner volume to receptors immobilized on the pore surface. Using a thin film of Ti metal for the anodization results in a nanotube array offering an even further enhanced inner surface and the possibility to apply electrical potentials via the resulting TiO2 semiconducting waveguide structure. Nanoporous substrates fabricated from SiNx thin films by colloid lithography, or made from SiO2 by e-beam lithography, will be presented as examples where the porosity is used to allow for the passage of ions in the case of tethered lipid bilayer membranes fused on top of the light-guiding layer, or the transport of protons through membranes used in fuel cell applications. The final example that we present concerns the replication of the nanopore structure by polymers in a process that leads to a nanorod array that is equally well suited to guide the light as the mold; however, it opens a totally new field for integrated optics formats for direct chemical and biomedical sensing with an extension to even molecularly imprinted structures. Graphical abstract.
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PEGylated nanoparticles have been extensively investigated in different platforms for drug delivery. However, the physiological effects related to platelet activation, and the potential procoagulant activity which could lead to thrombosis and further cardiovascular diseases have not been widely examined. In this work, we studied the effect of differentially charged PEGylated lipid-polymer nanoparticles in the human platelet aggregation and activation by light transmission aggregometry and flow cytometry. PEGylated nanoparticles inhibited the platelet aggregation with a dose dependency (350, 700, and 1400µg/mL) in both ADP- and collagen-induced platelet aggregation, and P-selectin expression. Charged nanoparticles (anionic and cationic) presented higher inhibitions of the platelet aggregation compared to neutral nanoparticles, and particularly the cationic particles generated a slightly higher effect. The obtained results demonstrated the safety of the differentially charged PEGylated lipid-polymer nanoparticles, and their ability to inhibit the aggregation and activation of human platelets stimulated by two classic platelet activators.
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Plaquetas/efectos de los fármacos , Portadores de Fármacos/farmacología , Lípidos/farmacología , Nanopartículas/química , Inhibidores de Agregación Plaquetaria/farmacología , Polietilenglicoles/farmacología , Plaquetas/citología , Portadores de Fármacos/efectos adversos , Portadores de Fármacos/química , Humanos , Lípidos/efectos adversos , Lípidos/química , Nanopartículas/efectos adversos , Activación Plaquetaria/efectos de los fármacos , Agregación Plaquetaria/efectos de los fármacos , Inhibidores de Agregación Plaquetaria/efectos adversos , Inhibidores de Agregación Plaquetaria/química , Polietilenglicoles/efectos adversos , Polietilenglicoles/químicaRESUMEN
The remarkably high intracellular concentration of reducing agents is an excellent endogenous stimulus for designing nanocarriers programmed for intracellular delivery of therapeutic agents. However, despite their excellent biodegradability profiles, aliphatic polyesters that are fully degradable in response to the intracellular reducing environment are rare. Herein, a reduction-responsive drug delivery nanocarrier derived from a linear polyester bearing disulfide bonds is reported. The reduction-responsive polyester is synthesized via a convenient polycondensation process. After conjugation of terminal carboxylic acid groups of polyester to polyethylene glycol (PEG), the resulting polymer self-assembles into nanoparticles that are capable of encapsulating dye and anticancer drug molecules. The reduction-responsive nanoparticles display a fast payload release rate in response to the intracellular reducing environment, which translates into superior anticancer activity towards PC-3 cells.
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Antineoplásicos/química , Polietilenglicoles/química , Polímeros/química , Antineoplásicos/farmacología , Supervivencia Celular/efectos de los fármacos , Portadores de Fármacos/química , Sistemas de Liberación de Medicamentos , Humanos , Masculino , Nanopartículas/química , Poliésteres/química , Neoplasias de la Próstata/tratamiento farmacológicoRESUMEN
Protein therapeutics have gained attention recently for treatment of a myriad of human diseases due to their high potency and unique mechanisms of action. We present the development of a novel polymeric thermosponge nanoparticle for efficient delivery of labile proteins using a solvent-free polymer thermo-expansion mechanism with clinical potential, capable of effectively delivering a range of therapeutic proteins in a sustained manner with no loss of bioactivity, with improved biological half-lives and efficacy in vivo.
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Antiinflamatorios/administración & dosificación , Preparaciones de Acción Retardada/química , Hipoglucemiantes/administración & dosificación , Insulina/administración & dosificación , Interleucina-10/administración & dosificación , Nanopartículas/química , Polímeros/química , Animales , Antiinflamatorios/farmacocinética , Antiinflamatorios/farmacología , Línea Celular , Sistemas de Liberación de Medicamentos , Humanos , Hipoglucemiantes/farmacocinética , Hipoglucemiantes/farmacología , Insulina/farmacocinética , Insulina/farmacología , Interleucina-10/farmacocinética , Interleucina-10/farmacología , Ratones , Nanopartículas/ultraestructura , TemperaturaRESUMEN
Selective tumor targeting and drug delivery are critical for cancer treatment. Stimulus-sensitive nanoparticle (NP) systems have been designed to specifically respond to significant abnormalities in the tumor microenvironment, which could dramatically improve therapeutic performance in terms of enhanced efficiency, targetability, and reduced side-effects. We report the development of a novel L-cysteine-based poly (disulfide amide) (Cys-PDSA) family for fabricating redox-triggered NPs, with high hydrophobic drug loading capacity (up to 25â wt% docetaxel) and tunable properties. The polymers are synthesized through one-step rapid polycondensation of two nontoxic building blocks: L-cystine ester and versatile fatty diacids, which make the polymer redox responsive and give it a tunable polymer structure, respectively. Alterations to the diacid structure could rationally tune the physicochemical properties of the polymers and the corresponding NPs, leading to the control of NP size, hydrophobicity, degradation rate, redox response, and secondary self-assembly after NP reductive dissociation. Inâ vitro and inâ vivo results demonstrate these NPs' excellent biocompatibility, high selectivity of redox-triggered drug release, and significant anticancer performance. This system provides a promising strategy for advanced anticancer theranostic applications.
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Cisteína/química , Nanopartículas/química , Polímeros/química , Antineoplásicos/administración & dosificación , Antineoplásicos/química , Antineoplásicos/toxicidad , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Disulfuros/química , Docetaxel , Portadores de Fármacos/química , Transferencia Resonante de Energía de Fluorescencia , Células HeLa , Humanos , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Neoplasias/tratamiento farmacológico , Oxidación-Reducción , Tamaño de la Partícula , Polietilenglicoles/química , Taxoides/administración & dosificación , Taxoides/química , Taxoides/toxicidad , Nanomedicina TeranósticaRESUMEN
The established ability of graphitic carbon-nanomaterials to undergo ambient condition Diels-Alder reactions with cyclopentadienyl (Cp) groups is herein employed to prepare fullerene-polythiophene covalent hybrids with improved electron transfer and film forming characteristics. A novel precisely designed polythiophene (M n 9.8 kD, D 1.4) with 17 mol% of Cp-groups bearing repeat unit is prepared via Grignard metathesis polymerization. The UV/Vis absorption and fluorescence (λex 450 nm) characteristics of polythiophene with pendant Cp-groups (λmax 447 nm, λe-max 576 nm) are comparable to the reference poly(3-hexylthiophene) (λmax 450 nm, λe-max 576 nm). The novel polythiophene with pendant Cp-groups is capable of producing solvent-stable free-standing polythiophene films, and non-solvent assisted self-assemblies resulting in solvent-stable nanoporous-microstructures. (1) H-NMR spectroscopy reveals an efficient reaction of the pendant Cp-groups with C60 . The UV/Vis spectroscopic analyses of solution and thin films of the covalent and physical hybrids disclose closer donor-acceptor packing in the case of covalent hybrids. AFM images evidence that the covalent hybrids form smooth films with finer lamellar-organization. The effect is particularly remarkable in the case of poorly soluble C60 . A significant enhancement in photo-voltage is observed for all devices constituted of covalent hybrids, highlighting novel avenues to developing efficient electron donor-acceptor combinations for light harvesting systems.
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Despite existing for millennia, tuberculosis (TB) remains a persistent global health challenge. A significant obstacle in controlling TB spread is the need for a rapid, portable, sensitive, and accurate diagnostic test. Currently, sputum culture stands as a benchmark test for TB diagnosis. Although highly reliable, it necessitates advanced laboratory facilities and involves considerable testing time. In this context, we present a rapid, portable, and cost-effective optical fiber sensor designed to measure lipoarabinomannan (LAM), a TB biomarker found in patients' urine samples. Our sensing approach is based on the applications of phase shift-cavity ringdown spectroscopy (PS-CRDS) to an optical fiber cavity created by two fiber Bragg gratings. A tapered fiber is spliced inside the optical cavity to serve as the sensing head. We functionalize the tapered fiber surface with anti-LAM antigen CS-35 through a unique chemistry, creating a strong affinity for LAM molecules. We measure the phase difference between the cavity transmission and the reference modulating signal at the cavity output. The measured phase is directly proportional to the injected LAM concentrations in aqueous solutions over the sensing head. Our demonstrated sensor provides a detection limit of 10 pg/mL and a sensitivity of 0.026°/pg/mL. This sensor holds promise for numerous applications in the healthcare sector, particularly in low-resource settings.
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Three new aromatic acids, named lahorenoic acids A (1), B (2), and C (3), have been isolated along with the known compounds phenazine-1-carboxylic acid (4), 2-hydroxyphenazine-1-carboxylic acid (5), 2-hydroxyphenazine (6), 2,8-dihydroxyphenazine (7), cyclo-Pro-Tyr (8), cyclo-Pro-Val (9), cyclo-Pro-Met (10), and WLIP (11) and characterized from the biocontrol strain Pseudomonas aurantiaca PB-St2. The structures of these compounds were deduced by 1D and 2D NMR spectroscopic and mass spectral data interpretation. Compounds 2, 4, and 7 showed moderate antibacterial activity against mycobacteria and other Gram-positive bacteria, while 4 was also found to exhibit cytotoxic and antifungal properties.
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Antifúngicos/aislamiento & purificación , Ácidos Carboxílicos/aislamiento & purificación , Pseudomonas/química , Antifúngicos/química , Antifúngicos/farmacología , Ácidos Carboxílicos/química , Ácidos Carboxílicos/farmacología , Bacterias Grampositivas/efectos de los fármacos , Estructura Molecular , Mycobacteriaceae/efectos de los fármacos , Resonancia Magnética Nuclear Biomolecular , Fenazinas/química , Fenazinas/aislamiento & purificación , Fenazinas/farmacologíaRESUMEN
Rational construction of interfaces based on multicomponent responsive systems in which molecular transport is mediated by structures of nanoscale dimensions has become a very fertile research area in biomimetic supramolecular chemistry. Herein, we describe the creation of hybrid mesostructured interfaces with reversible gate-like transport properties that can be controlled by chemical inputs, such as protons or calcium ions. This was accomplished by taking advantage of the surface-initiated polymerization of 2-(methacryloyloxy)ethyl phosphate (MEP) monomer units into and onto mesoporous silica thin films. In this way, phosphate-bearing polymer brushes were used as "gatekeepers" located not only on the outer surface of mesoporous thin films but also in the inner environment of the porous scaffold. Pore-confined PMEP brushes respond to the external triggering chemical signals not only by altering their physicochemical properties but also by switching the transport properties of the mesoporous film. The ion-gate response/operation was based on the protonation and/or chelation of phosphate monomer units in which the polymer brush works as an off-on switch in response to the presence of protons or Ca(2+) ions. The hybrid meso-architectured interface and their functional features were studied by a combination of experimental techniques including ellipso-porosimetry, cyclic voltammetry, X-ray reflectivity, grazing incidence small-angle X-ray scattering, X-ray photoelectron spectroscopy, and in situ atomic force microscopy. In this context, we believe that the integration of stimuli-responsive polymer brushes into nanoscopic supramolecular architectures would provide new routes toward multifunctional biomimetic nanosystems displaying transport properties similar to those encountered in biological ligand-gated ion channels.
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Materiales Biomiméticos/química , Canales Iónicos Activados por Ligandos/química , Membranas Artificiales , Polímeros/química , Biomimética/métodos , Calcio , Nanoestructuras , Fosfatos/química , Porosidad , ProtonesRESUMEN
This contribution summarizes efforts in designing, assembling/synthesizing, and structurally and functionally characterizing nanostructured materials using anodized aluminum oxide (AAO) as a thin-film template. Optical waveguide spectroscopy, using a nanoporous template as the guiding structure, is a particularly powerful analytical tool. The layer-by-layer approach for the fabrication of multilayer assemblies is shown to allow the fabrication of nanotube arrays. In addition to using dendrimers as building blocks, semiconducting nanomaterial (e.g., quantum dot) hybrid architectures with very interesting photophysical properties can be assembled. These can be employed, for example, in biosensing applications. Other strategies for using the AAO layers as templates include the growth of polymeric nanorod arrays from different functional monomers, which, after the dissolution of the template, are still able to guide light. This opens up novel concepts for integrated optics platforms with nanostructured materials.
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Nanoestructuras/química , Nanotecnología/métodos , Polímeros/química , Técnicas Biosensibles , Electrodos , PorosidadRESUMEN
The deposition of polyallylamine (PAA) adlayers by pulsed plasma polymerization on various types of polymeric substrates has been explored as a general route to amino functionalized polymeric surfaces. These amino groups are highly suitable for anchoring an atom transfer radical polymerization (ATRP) initiator via a robust amide linkage. Subsequent surface initiated ATRP (SI-ATRP) of monomethoxy oligo(ethylene glycol) methacrylate (MeOEGMA) resulted in polyMeOEGMA brush grafted polymer surfaces. This combined strategy of pulsed plasma polymerization with SI-ATRP was demonstrated for five different polymeric substrates namely polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), and polytetrafluoroethylene (PTFE). Analysis of brush layers by attenuated total reflection infrared (ATR-IR) spectroscopy as well as X-ray photoelectron spectroscopy (XPS) fully corroborated the success of the proposed strategy for all substrate types.
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Química Orgánica/métodos , Poliaminas/química , Polímeros/síntesis química , Metacrilatos/química , Polietilenglicoles/química , Polimerizacion , Polímeros/química , Propiedades de SuperficieRESUMEN
We demonstrate high-sensitivity biosensing by optical waveguide spectroscopy (OWS) at visible wavelengths using aligned polycyanurate thermoset nanorods (PCNs) arranged in extended arrays as waveguides. The PCNs formed by thermal polymerization of a cyanate ester monomer in self-ordered nanoporous alumina templates were 60 nm in diameter and 650 nm in length. Subtle refractive index changes of the medium surrounding the nanorods could be detected by monitoring the angular shifts of waveguiding modes. The sensing figure of merit thus achieved amounted to 196 reciprocal refractive index units and is, therefore, higher than that of other sensors based on angular modulation, while the configuration used here is eligible for further surface functionalization. Kinetics of the binding of taurine to the surface cyanate groups of the PCNs was monitored by OWS. Thus, modified PCNs bearing sulfonic acid groups at their surfaces were obtained. PCN arrays may represent a versatile platform for the design of biosensors.
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Técnicas Biosensibles , Nanotubos/química , Polímeros/química , Triazinas/química , Cinética , Propiedades de SuperficieRESUMEN
Development of low cost biosensing using convenient and environmentally benign materials is important for wide adoption and ultimately improved healthcare and sustainable development. Immobilized antibodies are often incorporated as an essential biorecognition element in point-of-care biosensors but these proteins are costly. We present a strategy of combining convenient and low-cost surface functionalization approaches for increasing the overall binding activity of antibody functionalized natural and synthetic fibers. We demonstrate a simple one-step in situ silica NP growth protocol for increasing the surface area available for functionalization on cotton and polyester fabrics as well as on nanoporous cellulose substrates. Comparing this effect with the widely adopted and low cost plant-based polyphenol coating to enhance antibody immobilization, we find that both approaches can similarly increase overall surface activity, and we illustrate conditions under which the two approaches can produce an additive effect. Furthermore, we introduce co-immobilization of antibodies with a sacrificial "steric helper" protein for further enhancing surface activities. In combination, several hundred percent higher activities compared to physical adsorption can be achieved while maintaining a low amount of antibodies used, thus paving a practical path towards low cost biosensing.
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Molecular design of ionic current rectifiers created on the basis of single conical nanopores is receiving increasing attention by the scientific community. Part of the appeal of this topic relies on the interest in sensors and fluidic nanoactuators based on the transport of ions and molecules through nanopore architectures that can readily be integrated into functional systems. The chemical modification of the pore walls controls not only the diameter of these nanoarchitectures but also their selectivity and transport properties. In order to confer selectivity to solid-state nanopores, it is necessary to develop and explore new methods for functionalizing the pore walls. Hence, the creation of functional nanopores capable of acting as selective ion channels or smart nanofluidic sensors depends critically on our ability to assemble and build up molecular architectures in a predictable manner within confined geometries with dimensions comparable to the size of the building blocks themselves. In this context, layer-by-layer deposition of polyelectrolytes offers a straightforward process for creating nanoscopic supramolecular assemblies displaying a wide variety of functional features. In this work, we describe for the first time the integration of layer-by-layer polyelectrolyte assemblies into single conical nanopores in order to study and explore the functional features arising from the creation of charged supramolecular assemblies within the constrained geometry of the nanofluidic device. To address this challenging topic, we used a combined experimental and theoretical approach to elucidate and quantify the electrostatic changes taking place inside the nanopore during the supramolecular assembly process. The multilayered films were built up through consecutive layer-by-layer adsorption of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) on the pore surface. Our results show that the charge transport properties of single conical nanopores functionalized with PAH/PSS assemblies are highly dependent on the number of layers assembled on the pore wall. In contrast to what happens with PAH/PSS films deposited on planar surfaces (quantitative charge reversal), the surface charge of the pore walls decreases dramatically with the number of PAH/PSS layers assembled into the nanopore. This behavior was attributed to the nanoconfinement-induced structural reorganization of the polyelectrolyte layers, leading to the efficient formation of ion pairs and promoting a marked decrease in the net fixed charges on the nanopore walls. We consider that these results are of paramount relevance for the modification of nanopores, nanopipets, and nanoelectrodes using charged supramolecular assemblies, as well as of importance in "soft nanotechnology" provided that structural complexity, induced by nanoconfinement, can define the functional properties of self-assembled polymeric nanostructures.
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A robust and straightforward strategy allowing the controlled confinement of metal nanoparticles within the 3D framework of mesoporous films is presented. The chemical methodology is based on the inner surface modification of mesoporous silica films with polyelectrolyte brushes. We demonstrate that the macromolecular building blocks significantly enhance the site-selective preconcentration of nanoparticle precursors in the inner environment of the mesoporous film. Then, chemical reduction of the preconcentrated precursors led to the formation of metal nanoparticles locally addressed in the mesoporous structure. We show that the synergy taking place between two versatile functional nanobuilding blocks (ordered mesocavities and polymer brushes) can produce stable embedded nanoparticles with tuned optical properties in a very simple manner. As a general framework, the strategy can be easily adapted to different sets of polymer brushes and mesoporous films in order to regulate the monomer-precursor interactions and, consequently, manipulate the site-selective character of the different chemistries taking place in the film. We consider that the "integrative chemistry" approach described in this work provides new pathways to manipulate the physicochemical characteristics of hybrid organic-inorganic advanced functional assemblies based on the rational design of chemistry and topology in confined environments.
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The creation of switchable and tunable nanodevices displaying transport properties similar to those observed in biological pores poses a major challenge in molecular nanotechnology. Here, we describe the construction of a fully "abiotic" nanodevice whose transport properties can be accurately controlled by manipulating the proton concentration in the surrounding environment. The ionic current switching characteristics displayed by the nanochannels resemble the typical behavior observed in many biological channels that fulfill key pH-dependent transport functions in living organisms, that is, the nanochannel can be switched from an "off" state to an "on" state in response to a pH drop. The construction of such a chemical nanoarchitecture required the integration of stable and ductile macromolecular building blocks constituted of pH-responsive poly(4-vinyl pyridine) brushes into solid state nanopores that could act as gate-keepers managing and constraining the flow of ionic species through the confined environment. In this context, we envision that the integration of environmental stimuli-responsive brushes into solid-state nanochannels would provide a plethora of new chemical alternatives for molecularly design robust signal-responsive "abiotic" devices mimicking the function of proton-gated ion channels commonly encountered in biological membranes.