Mesoporous Gold: Substrate-Dependent Growth Dynamics, Strain Accumulation, and Electrocatalytic Activity for Biosensing.

Understanding the growth of mesoporous crystalline materials, such as mesoporous metals, on different substrates can provide valuable insights into the crystal growth dynamics and the redox reactions that influence their electrochemical sensing performance. Herein, it is demonstrated how the amorphous nature of the glass substrate can suppress the typical <111> oriented growth in mesoporous Au (mAu) films. The suppressed <111> growth is manifested as an accumulation of strain, leading to the generation of abundant surface defects, which are beneficial for enhancing the electrochemical activity. The fine structuring attained enables dramatically accelerated diffusion and enhances the electrochemical sensing performance for disease-specific biomolecules. As a proof-of-concept, the as-fabricated glass-grown mAu film demonstrates high sensitivity in electrochemical detection of SARS-CoV-2-specific RNA with a limit of detection (LoD) as low as 1 attomolar (aM).

Nanoarchitecture Frameworks for Electrochemical miRNA Detection.

With revolutionary advances in next-generation sequencing, the human transcriptome has been comprehensively interrogated. These discoveries have highlighted the emerging functional and regulatory roles of a large fraction of RNAs suggesting the potential they might hold as stable and minimally invasive disease biomarkers. Although a plethora of molecular-biology- and biosensor-based RNA-detection strategies have been developed, clinical application of most of these is yet to be realized. Multifunctional nanomaterials coupled with sensitive and robust electrochemical readouts may prove useful in these applications. Here, we summarize the major contributions of engineered nanomaterials-based electrochemical biosensing strategies for the analysis of miRNAs. With special emphasis on nanostructure-based detection, this review also chronicles the needs and challenges of miRNA detection and provides a future perspective on the presented strategies.

Hydrogel Nanoarchitectonics: An Evolving Paradigm for Ultrasensitive Biosensing.

The integration of nanoarchitectonics and hydrogel into conventional biosensing platforms offers the opportunities to design physically and chemically controlled and optimized soft structures with superior biocompatibility, better immobilization of biomolecules, and specific and sensitive biosensor design. The physical and chemical properties of 3D hydrogel structures can be modified by integrating with nanostructures. Such modifications can enhance their responsiveness to mechanical, optical, thermal, magnetic, and electric stimuli, which in turn can enhance the practicality of biosensors in clinical settings. This review describes the synthesis and kinetics of gel networks and exploitation of nanostructure-integrated hydrogels in biosensing. With an emphasis on different integration strategies of hydrogel with nanostructures, this review highlights the importance of hydrogel nanostructures as one of the most favorable candidates for developing ultrasensitive biosensors. Moreover, hydrogel nanoarchitectonics are also portrayed as a promising candidate for fabricating next-generation robust biosensors.

Recent progress of functional metal-organic framework materials for water treatment using sulfate radicals.

Human health is being threatened by the ever-increasing water pollution. Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) are rapidly being developed and gaining considerable attention due to their high oxidation potential and selectivity as a way to purify water by degrading organic contaminants in it. Among the catalytic materials that can activate the precursor to generate SO4•-, metal-organic frameworks (MOFs) are the most promising heterogeneous catalytic material in SR-AOPs because of their various structure possibilities, large surface area, ordered porous structure, and regular activation sites. Herein, an in-depth overview of MOFs and their derivatives for water purification with SR-AOPs is provided. The latest studies on pristine MOFs, MOF composites, and MOF derivatives (metal oxides, metal-carbon hybrids, and carbon materials) are summarized. The mechanisms of decomposition of pollutants in water via radical and non-radical pathways are also discussed. This review suggests future research directions for water purification through MOF-based SR-AOP.

Cu-based MOF-derived architecture with Cu/Cu2O nanospheres anchored on porous carbon nanosheets for efficient capacitive deionization.

The design of high-performance electrode materials with excellent desalination ability has always been a research goal for efficient capacitive deionization (CDI). Herein, a hybrid architecture with Cu/Cu2O nanospheres anchored on porous carbon nanosheets (Cu/Cu2O/C) was first synthesized by pyrolyzing a two-dimensional (2D) Cu-based metal-organic framework and then evaluated as a cathode for hybrid CDI. The as-prepared Cu/Cu2O/C exhibits a hierarchically porous structure with a high specific surface area of 305 m2 g-1 and large pore volume of 0.55 cm3 g-1, which is favorable to accelerating ion migration and diffusion. The porous carbon nanosheet matrix with enhanced conductivity will facilitate the Faradaic reactions of Cu/Cu2O nanospheres during the desalination process. The Cu/Cu2O/C hybrid architecture displays a high specific capacitance of 142.5 F g-1 at a scan rate of 2 mV s-1 in 1 M NaCl solution. The hybrid CDI constructed using the Cu/Cu2O/C cathode and a commercial activated carbon anode exhibits a high desalination capacity of 16.4 mg g-1 at an operation voltage of 1.2 V in 500 mg L-1 NaCl solution. Additionally, the hybrid CDI exhibits a good cycling stability with 18.3% decay in the desalination capacity after 20 electrosorption-desorption cycles. Thus, the Cu/Cu2O/C composite is expected to be a promising cathode material for hybrid CDI.

Extracellular Vesicle Nanoarchitectonics for Novel Drug Delivery Applications.

Extracellular vesicles (EVs) can transfer intercellular messages in various (patho)physiological processes and transport biomolecules to recipient cells. EVs possess the capacity to evade the immune system and remain stable over long periods, identifying them as natural carriers for drugs and biologics. However, the challenges associated with EVs isolation, heterogeneity, coexistence with homologous biomolecules, and lack of site-specific delivery, have impeded their potential. In recent years, the amalgamation of EVs with rationally engineered nanostructures has been proposed for achieving effective drug loading and site-specific delivery. With the advancement of nanotechnology and nanoarchitectonics, different nanostructures with tunable size, shapes, and surface properties can be integrated with EVs for drug loading, target binding, efficient delivery, and therapeutics. Such integration may enable improved cellular targeting and the protection of encapsulated drugs for enhanced and specific delivery to target cells. This review summarizes the recent development of nanostructure amalgamated EVs for drug delivery, therapeutics, and real-time monitoring of disease progression. With a specific focus on the exosomal cargo, diverse drug delivery system, and biomimetic nanostructures based on EVs for selective drug delivery, this review also chronicles the needs and challenges of EV-based biomimetic nanostructures and provides a future outlook on the strategies posed.

Electrochemical Synthesis of Mesoporous Architectured Ru Films Using Supramolecular Templates.

The electrochemical synthesis of mesoporous ruthenium (Ru) films using sacrificial self-assembled block polymer micelles templates, and its electrochemical surface oxidation to RuOx is described. Unlike standard methods such as thermal oxidation, the electrochemical oxidation method described here retains the mesoporous structure. Ru oxide materials serve as high-performance supercapacitor electrodes due to their excellent pseudocapacitive behavior. The mesoporous architectured film shows superior specific capacitance (467 F g-1Ru ) versus a nonporous Ru/RuOx electrode (28 F g-1Ru ) that is prepared via the same method but omitting the pore-directing polymer. Ultrahigh surface area materials will play an essential role in increasing the capacitance of this class of energy storage devices because the pseudocapacitive redox reaction occurs on the surface of electrodes.

Nanostructured mesoporous gold electrodes detect protein phosphorylation in cancer with electrochemical signal amplification.

Protein phosphorylation is a post-translational modification of kinase proteins that changes a protein's conformation to regulate crucial biological functions. However, the phosphorylation of protein is significantly altered during cancer progression which triggers abnormal cellular pathways and this phosphorylation can serve as an emergent diagnostic and prognostic biomarker for cancer. Herein, we develop a nanostructured mesoporous gold electrode (NMGE)-based biosensor that enables a highly sensitive detection of protein phosphorylation with electrochemical signal amplification. The biosensor comprises nanostructured mesoporous gold electrodes whose electro-conductive framework is superior to that of the nonporous electrodes. We characterize our developed nano/mesoporous gold electrode with various electrochemical methods in the presence of the [Fe(CN)6]3-/4- redox system. We find that the mesoporous gold electrode catalyzes both the oxidation and reduction processes of the [Fe(CN)6]3-/4- system and generates a current signal that is 3 times higher than that of the nonporous gold electrode. This superior signal transduction of our nano/mesoporous gold electrode is enabled through a pore-induced (i) high electrochemically active surface area and (ii) reduced impedance with a high signal to noise ratio. The assay utilizes direct adsorption of an immunoprecipitated purified BRAF protein towards the mesoporous gold electrode and thus avoids the cumbersome sensor surface functionalization. Our developed biosensor detects the phosphorylated BRAF protein with a 2.5-fold increase in sensitivity and an ≈10-fold increase in the limit of detection (LOD) in comparison with the nonporous gold electrodes. The assay also works on a wide dynamic range from 0.5 to 20 ng µL-1 of the protein which further shows its potential for clinical application. We envisage that this nanostructured mesoporous gold biosensor will be of high interest for clinical application.

Effect of N2 flow rate on kinetic investigation of lignin pyrolysis.

Fast pyrolysis of lignin can obtain valuable products such as bio-oil, bio-chemical, syngas, and biochar. In this study, two types of lignin known as brown solid from the byproduct of cellulosic ethanol fermentation and commercial dealkaline lignin from the papermaking process were used for pyrolysis in a 3-L batch reactor at 300-450 °C. The product composition in the liquid and gas phases were analyzed by using gas chromatography-mass spectrometry/Flame-ionization detector/thermal conductivity detector (GC-MS/FID/TCD). Increasing the N2 flow rate to 150 mL/min was sufficient to increase the production of bio-oil/bio-organics up to 15% for brown solid pyrolysis. In contrast, the biochemical production during dealkaline lignin pyrolysis was not sensitive to the change of the N2 flow rate. The amount of biochar produced in the pyrolysis (~60%) slightly changed at various pyrolysis temperature and gas flow rate, which could be due to the relatively low pyrolysis temperature that was insufficient to decompose the lignin. The GC-MS analysis also revealed that C7-C8 compounds, which represented the phenolic compounds, were the most abundant in the liquid products. Kinetic models of the pyrolysis were established based on the thermogravimetric analysis.

Superparamagnetic nanoarchitectures for disease-specific biomarker detection.

The detection of clinically relevant disease-specific biomolecules, including nucleic acids, circulating tumor cells, proteins, antibodies, and extracellular vesicles, has been indispensable to understand their functions in disease diagnosis and prognosis. Therefore, a biosensor for the robust, ultrasensitive, and selective detection of these low-abundant biomolecules in body fluids (blood, urine, and saliva) is emerging in current clinical research. In recent years, nanomaterials, especially superparamagnetic nanomaterials, have played essential roles in biosensing due to their intrinsic magnetic, electrochemical, and optical properties. However, engineered multicomponent magnetic nanoparticle-based current biosensors that offer the advantages of excellent stability in a complex biomatrix; easy and alterable biorecognition of ligands, antibodies, and receptor molecules; and unified point-of-care integration have yet to be achieved. This review introduces the recent advances in superparamagnetic nanostructures for electrochemical and optical biosensing for disease-specific biomarkers. This review emphasizes the synthesis, biofunctionalization, and intrinsic properties of nanomaterials essential for robust, ultrasensitive biosensing. With a particular emphasis on nanostructure-based electrochemical and optical detection of disease-specific biomarkers such as nucleic acids (DNA and RNA), proteins, autoantibodies, and cells, this review also chronicles the needs and challenges of nanoarchitecture-based detection. These summaries provide further insights for researchers to inspire their future work on the development of nanostructures for integrating into biosensing and devices for a broad field of applications in analytical sensing and in clinic.

Avoiding Pre-Isolation Step in Exosome Analysis: Direct Isolation and Sensitive Detection of Exosomes Using Gold-Loaded Nanoporous Ferric Oxide Nanozymes.

Most of the current exosome-analysis strategies are time-consuming and largely dependent on commercial extraction kit-based preisolation step, which requires extensive sample manipulations, costly isolation kits, reagents, tedious procedures, and sophisticated equipment and is prone to bias/artifacts. Herein we introduce a simple method for direct isolation and subsequent detection of a specific population of exosomes using an engineered superparamagnetic material with multifunctional properties, namely, gold-loaded ferric oxide nanocubes (Au-NPFe2O3NC). In this method, the Au-NPFe2O3NC were initially functionalized with a generic tetraspanin (exosomes-associated) antibody (i.e., CD63) and dispersed in sample fluids where they work as "dispersible nanocarriers" to capture the bulk population of exosomes. After magnetic collection and purification, Au-NPFe2O3NC-bound exosomes were transferred to the tissue-specific, antibody-modified, screen-printed electrode. As a proof of principle, we used a specific placental marker, placenta alkaline phosphatase (PLAP), to detect exosomes secreted from placental cells. The peroxidase-like activity of Au-NPFe2O3NC was then used to accomplish an enzyme-linked immunosorbent assay (ELISA)-based sensing protocol for naked-eye observation along with UV-visible and electrochemical detection of PLAP-specific exosomes present in placental cell-conditioned media. We demonstrated excellent agreement in analytical performance for the detection of placental cell-derived exosomes (i.e., linear dynamic range, 103-107 exosomes/mL; limit of detection, 103 exosomes/mL; relative standard deviation (%RSD) of <5.5% for n = 3) using with and without commercial "total exosome isolation kit"-based preisolation step. We envisage that this highly sensitive, rapid, and inexpensive assay could be useful in quantifying specific populations of exosomes for various clinical applications, focusing on pregnancy complications.

Fabrication of Nanoporous Carbon Materials with Hard- and Soft-Templating Approaches: A Review.

Hard- and soft-templating approaches are one of potential strategies for the fabrication of functional nanoporous carbon materials with desired morphologies and properties. Enormous efforts have been paid for understanding the synthetic mechanisms that strongly influence the materials design and applications. All of these investigations are crucial to encourage the application of hard- and soft-templating approaches for the precise synthesis of nanoporous carbon materials. In this review, we mainly summarize significant works employing different synthetic methods for making carbon materials with various pore sizes and functionalities. The content of the review article contains: (i) Hard-templating synthesis of microporous carbon from zeolites; (ii) Hard-templating synthesis of mesoporous carbon from mesoporous silica; (iii) Hard-templating synthesis of macroporous carbon; and (iv) Soft-templating synthesis of mesoporous carbon. This review aims to provide a detailed glimpse of hard- and soft-templating approaches for future development of functional nanoporous carbon materials.

Biological Functions and Current Advances in Isolation and Detection Strategies for Exosome Nanovesicles.

Exosomes are nanoscale (≈30-150 nm) extracellular vesicles of endocytic origin that are shed by most types of cells and circulate in bodily fluids. Exosomes carry a specific composition of proteins, lipids, RNA, and DNA and can work as cargo to transfer this information to recipient cells. Recent studies on exosomes have shown that they play an important role in various biological processes, such as intercellular signaling, coagulation, inflammation, and cellular homeostasis. These functional roles are attributed to their ability to transfer RNA, proteins, enzymes, and lipids, thereby affecting the physiological and pathological conditions in various diseases, including cancer and neurodegenerative, infectious, and autoimmune diseases (e.g., cancer initiation, progression, and metastasis). Due to these unique characteristics, exosomes are considered promising biomarkers for the diagnosis and prognosis of various diseases via noninvasive or minimally invasive procedures. Over the last decade, a plethora of methodologies have been developed for analyzing disease-specific exosomes using optical and nonoptical tools. Here, the major biological functions, significance, and potential role of exosomes as biomarkers and therapeutics are discussed. Furthermore, an overview of the most commonly used techniques for exosome analysis, highlighting the major technical challenges and limitations of existing techniques, is presented.

Preparation of Ultraviolet Curing Type Silicone Rubbers Containing Mesoporous Silica Fillers.

Here we have been focusing on mesoporous silica (MPS) as inorganic filler material to improve the mechanical strength of silicone rubbers. The MPS particles are more effective in reducing the coefficient of thermal expansion (CTE) and hardening silicone rubber composites when compared to commercially available nonporous silica particles. In this study, we utilize ultraviolet curing type silicone rubbers and prepare MPS composites according to a simple single-step method. From an industrial viewpoint, simplifying the fabrication processes is critical. The thermal stability and mechanical strength are examined in detail in order to showcase the effectiveness of MPS particles as filler materials.

Tuning Wall Thicknesses in Mesoporous Silica Films for Optimization of Optical Anti-Reflective Properties.

This work reports the fabrication of mesoporous silica films with controllable wall thicknesses by spin coating of precursor solutions consisting of polystyrene-block-polybutadiene-block-polystyrene based triblock copolymers (Hydrogenated methyl Styrene Ethylene Butadiene methyl Styrene, HmSEBmS) and tetraethyl orthosilicate (TEOS) followed by calcination in air at 600 °C, for optical anti-reflection films. By changing the relative weight of the triblock polymer to TEOS, the pore-to-pore distance in the mesoporous silica film can be controlled without significantly affecting the size of the mesopores, thus, enabling effective control of the refractive index and porosity of the films. In terms of optical properties, the transmittance of the fabricated mesoporous silica film is approximately 3.3% higher than that of the uncoated glass substrate in the wavelength range of 400 to 750 nm.

Gold-Loaded Nanoporous Ferric Oxide Nanocubes with Peroxidase-Mimicking Activity for Electrocatalytic and Colorimetric Detection of Autoantibody.

The enzyme-mimicking activity of iron oxide based nanostructures has provided a significant advantage in developing advanced molecular sensors for biomedical and environmental applications. Herein, we introduce the horseradish peroxidase (HRP)-like activity of gold-loaded nanoporous ferric oxide nanocubes (Au-NPFe2O3NC) for the development of a molecular sensor with enhanced electrocatalytic and colorimetric (naked eye) detection of autoantibodies. The results showed that Au-NPFe2O3NC exhibits enhanced peroxidase-like activity toward the catalytic oxidation of 3,3',5,5'-tertamethylbenzidine (TMB) in the presence of H2O2 at room temperature (25 °C) and follows the typical Michaelis-Menten kinetics. The autoantibody sensor based on this intrinsic property of Au-NPFe2O3NC resulted in excellent detection sensitivity [limit of detection (LOD) = 0.08 U/mL] and reproducibility [percent relative standard deviation (% RSD) = <5% for n = 3] for analyzing p53-specific autoantibodies using electrochemical and colorimetric (naked eye) readouts. The clinical applicability of the sensor has been tested in detecting p53-specific autoantibody in plasma obtained from patients with epithelial ovarian cancer high-grade serous subtype (EOCHGS, number of samples = 2) and controls (benign, number of samples = 2). As Au-NPFe2O3NC possess high peroxidase-like activity for the oxidation of TMB in the presence of H2O2 [TMB is a common chromogenic substrate for HRP in enzyme-linked immunosorbent assays (ELISAs)], we envisage that our assay could find a wide range of application in developing ELISA-based sensing approaches in the fields of medicine (i.e., detection of other biomarkers the same as p53 autoantibody), biotechnology, and environmental sciences.

Facile synthesis of nanoporous Li1+xV1-xO2@C composites as promising anode materials for lithium-ion batteries.

Recently, a layered material with composition Li1+xV1-xO2 has been discovered as a promising alternative anode material to graphite due to its high volumetric capacity and low operation potential. Herein, we demonstrate a mild and cost-effective synthetic methodology to construct a novel nanoporous anode material (P-LVO@C), comprising Li1+xV1-xO2 nanocrystals embedded in a porous carbon matrix. The thermal decomposition of organic materials, including a triblock copolymer (P123) and citric acid, in a N2 atmosphere is the source of the nanoporous carbon in the porous composite material, while citric acid also plays a crucial role in maintaining the reductive environment of the synthetic medium. Due to the novel composition of Li1+xV1-xO2 (x ≥ 0.03), as well as its porous structure and well-integrated conductive framework, our P-LVO@C has great applicability as a high performance anode material for lithium-ion batteries. Our P-LVO@C composite electrode shows high reversible capacity with an excellent cycling performance (100 cycles) and good capacity retention (82%) at a higher rate (0.48C).

Correction: Zeolitic imidazolate framework (ZIF-8) derived nanoporous carbon: the effect of carbonization temperature on the supercapacitor performance in an aqueous electrolyte.

Correction for 'Zeolitic imidazolate framework (ZIF-8) derived nanoporous carbon: the effect of carbonization temperature on the supercapacitor performance in an aqueous electrolyte' by Christine Young et al., Phys. Chem. Chem. Phys., 2016, 18, 29308-29315.

Synthesis of Carbon Nanospheres Through Carbonization of Areca nut.

We demonstrate a bio-inspired one-pot synthesis of carbon nanospheres with micro-porosity achieved from a promising carbon-rich source (Areca nut) using direct pyrolysis in nitrogen atmosphere at 550 °C in a tube-furnace without adding any catalysts. The resultant carbon spheres are highly monodispersed, uniformly shaped and possess good absorption behaviour (10.5 mg · g−1) for methylene blue (MB).

Layer-by-Layer Motif Architectures: Programmed Electrochemical Syntheses of Multilayer Mesoporous Metallic Films with Uniformly Sized Pores.

Although multilayer films have been extensively reported, most compositions have been limited to non-catalytically active materials (e.g. polymers, proteins, lipids, or nucleic acids). Herein, we report the preparation of binder-free multilayer metallic mesoporous films with sufficient accessibility for high electrocatalytic activity by using a programmed electrochemical strategy. By precisely tuning the deposition potential and duration, multilayer mesoporous architectures consisting of alternating mesoporous Pd layers and mesoporous PdPt layers with controlled layer thicknesses can be synthesized within a single electrolyte, containing polymeric micelles as soft templates. This novel architecture, combining the advantages of bimetallic alloys, multilayer architectures, and mesoporous structures, exhibits high electrocatalytic activity for both the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR).