A rapid and ultrasensitive cardiac troponin I aptasensor based on an ion-sensitive field-effect transistor with extended gate.

Acute myocardial infarction (AMI) is a life-threatening disease with a short course and a high mortality rate. However, it is still a great challenge to achieve the on-site diagnosis of this disease within minutes, meaning there is an urgent need to develop an efficient technology for realizing the rapid diagnosis and early warning of AMI in clinical emergencies. In this study, an ultrasensitive electrochemical aptasensor based on an extended-gate ion-sensitive field-effect transistor (EGISFET) was designed to achieve the quantitative assay of cardiac troponin I (cTnI), which is a highly sensitive and specific biomarker of AMI, within only 5 min. The EGISFET exhibits extremely high detection sensitivity due to its separated structure with a large sensing area and the surface-modified Prussian blue-gold nanoparticles (PB-AuNPs) composite, which serves as a signal magnifier and DNA loading platform for good electrocatalytic ability with a large specific area. Additionally, a target-induced strand-release strategy is proposed to shorten the recognition time of cTnI using a particular DNA strand. Under optimal conditions, the as-prepared aptasensor exhibits a wide linear range of 1-1000 pg/mL, an ultralow detection limit of 0.3 pg/mL, and reliable detection results in real serum samples. It is highly anticipated that this EGISFET-based aptasensor will have broad applications in the early warning and rapid diagnosis of AMI and other acute diseases in emergency treatment.

Systemic regulation of binding sites in porous coordination polymers for ethylene purification from ternary C2 hydrocarbons.

The global demand for poly-grade ethylene (C2H4) is increasing annually. However, the energy-saving purification of this gas remains a major challenge due to the similarity in molecular properties among the ternary C2 hydrocarbons. To address this challenge, we report an approach of systematic tuning of the pore environment with organic sites (from -COOH to -CF3, then to -CH3) in porous coordination polymers (PCPs), of which NTU-73-CH3 shows remarkable capability for the direct production of poly-grade C2H4 from ternary C2 hydrocarbons under ambient conditions. In comparison, the precursor structure of NTU-73-COOH is unable to purify C2H4, while NTU-73-CF3 shows minimal ability to harvest C2H4. This is because the changed binding sites in the NTU-73-series not only eliminate the channel obstruction caused by the formation of gas clusters, but also enhance the interaction with acetylene (C2H2) and ethane (C2H6), as validated by in situ crystallographic and Raman analysis. Our findings, in particular the systematic tuning of the pore environment and the efficient C2H4 purification by NTU-73-CH3, provide a blueprint for the creation of advanced porous families that can handle desired tasks.

Confined-Coordination Induced Intergrowth of Metal-Organic Frameworks into Precise Molecular Sieving Membranes.

Metal-organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect-free high-connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined-coordination induced intergrowth strategy to fabricate lattice-defect-free Zr-MOF membrane towards precise molecular separation. The confined-coordination space properties (size and shape) and environment (water or DMF) were regulated to slow down the coordination reaction rate via controlling the counter-diffusion of MOF precursors (metal cluster and ligand), thereby inter-growing MOF crystals into integrated membrane. The resulting Zr-MOF membrane with angstrom-sized lattice apertures exhibits excellent separation performance both for gas separation and water desalination process. It was achieved H2 permeance of ~1200 GPU and H2/CO2 selectivity of ~67; water permeance of ~8 L ⋅ m-2 ⋅ h-1 ⋅ bar-1 and MgCl2 rejection of ~95 %, which are one to two orders of magnitude higher than those of state-of-the-art membranes. The molecular transport mechanism related to size-sieving effect and transition energy barrier differential of molecules and ions was revealed by density functional theory calculations. Our work provides a facile approach and fundamental insights towards developing precise molecular sieving membranes.

MnFe@N-CNTs Based Lactate Biomicrochips for Nonintrusive and Onsite Periodontitis Diagnosis.

In clinical settings, saliva has been established as a straightforward, noninvasive medium for diagnosing periodontitis. However, the precise diagnosis is often hampered by the absence of a specialized analyzer capable of detecting low concentrations of biomarkers typically found in saliva. In this study, we present a noninvasive, on-site screen-printed biomicrochip specifically engineered for the precise and sensitive quantification of lactate concentrations in saliva, a critical biomarker in the diagnosis of periodontitis. The microchip is constructed using a nanostructured ink formulation that includes MnFe@N-doped carbon nanotubes (MnFe@N-CNTs). These MnFe@N-CNTs exhibit a high degree of graphitization and low electrical resistance, significantly augmenting the electrocatalytic efficiency of the enzymatic reaction of lactate. This results in doubled sensitivity and a detection limit that surpasses those of the current advanced salivary assay methods. Remarkably, within just 30 s, the biomicrochip can quantitatively and precisely measure lactate concentrations in the saliva of 10 patients, which provides valuable insights into the severity of their periodontitis. This biosensor holds excellent potential for large-scale production and could broaden the scope of biomarker recognition, paving the way for the analysis of a wider range of oral diseases.

Nanomaterials-based electrochemical biosensors for diagnosis of COVID-19.

Since the outbreak of corona virus disease 2019 (COVID-19), this pandemic has caused severe death and infection worldwide. Owing to its strong infectivity, long incubation period, and nonspecific symptoms, the early diagnosis is essential to reduce risk of the severe illness. The electrochemical biosensor, as a fast and sensitive technique for quantitative analysis of body fluids, has been widely studied to diagnose different biomarkers caused at different infective stages of COVID-19 virus (SARS-CoV-2). Recently, many reports have proved that nanomaterials with special architectures and size effects can effectively promote the biosensing performance on the COVID-19 diagnosis, there are few comprehensive summary reports yet. Therefore, in this review, we will pay efforts on recent progress of advanced nanomaterials-facilitated electrochemical biosensors for the COVID-19 detections. The process of SARS-CoV-2 infection in humans will be briefly described, as well as summarizing the types of sensors that should be designed for different infection processes. Emphasis will be supplied to various functional nanomaterials which dominate the biosensing performance for comparison, expecting to provide a rational guidance on the material selection of biosensor construction for people. Finally, we will conclude the perspective on the design of superior nanomaterials-based biosensors facing the unknown virus in future.

Facile construction of nanocubic Mn3[Fe(CN)6]2@Pt based electrochemical DNA sensors for ultrafast precise determination of SARS-CoV-2.

Owing to the high mortality and strong infection ability of COVID-19, the early rapid diagnosis is essential to reduce the risk of severe symptoms and the loss of lung function. In clinic, the commonly used detection methods, including the computed tomography (CT) and reverse transcription-polymerase chain reaction (RT-PCR), are often time-consuming with bulky instruments, which normally require more than one hour to report the results. To shorten the analytical period for testing the COVID-19 virus (SARS-CoV-2), we proposed an ultrafast and ultrasensitive DNA sensors to achieve an accurate determination of the DNA sequence by the RNA reverse transcription (rtDNA) of the SARS-CoV-2. A nanocubic architecture of the MnFe@Pt crystals was constructed to integrate both electrocatalysis and conductivity to greatly improve the biosensing performance. After the immobilization of a specific capture and report DNA on above nanocomposite, the rtDNA can be rapidly caught to the DNA sensor to form a double-helix structure, thus generating the current signal change. Within only 10 min, the as-prepared DNA sensors exhibited ultralow detection limit (1 × 10-20 M) and wide linear detection range, together with an outstanding selectivity among various interfering substances.

Homoporous polydimethylsiloxane membrane microfilter for ultrafast label-free isolation and recognition of circulating tumor cells in peripheral blood.

The detection of circulating tumor cells (CTCs) in peripheral blood is a novel and accurate technique for the early diagnosis of cancers. However, this method is challenging because of the need for high collection efficiency due to the ultralow content and similar size of CTCs compared with other blood cells. To address the aforementioned issue, we proposed a homoporous polydimethylsiloxane (PDMS) membrane and its microfilter device to perform the ultrafast isolation and identification of CTCs directly from peripheral blood without any labeling treatment. The membrane pores can be homogenously controlled at a size of 6.3 µm through the cross-linking time of PDMS during a filtration-coating strategy. Within only 10 s, the designed device achieved a retention rate greater than 70% for pancreatic cancer cells, and it exhibited excellent cell compatibility to support cell proliferation. The isolated CTCs on this membrane can be easily observed and identified using a fluorescence microscope.

Delicate Softness in a Temperature-Responsive Porous Crystal for Accelerated Sieving of Propylene/Propane.

Soft nanoporous crystals with structural dynamics are among the most exciting recently discovered materials. However, designing or controlling a porous system with delicate softness that can recognize similar gas pairs, particularly for the promoted ability at increased temperature, remains a challenge. Here, we report a soft crystal (NTU-68) with a one-dimensional (1D) channel that expands and contracts delicately around 4 Å at elevated temperature. The completely different adsorption processes of propane (C3H8: kinetic dominance) and propylene (C3H6: thermodynamic preference) allow the crystal to show a sieving separation of this mixtures (9.9 min·g-1) at 273 K, and the performance increases more than 2-fold (20.4 min·g-1) at 298 K. This phenomenon is contrary to the general observation for adsorption separation: the higher the temperature, the lower the efficiency. Gas-loaded in situ powder X-ray analysis and modeling calculations reveal that slight pore expansion caused by the increased temperature provides plausible nanochannel for adsorption of the relatively smaller C3H6 while maintaining constriction on the larger C3H8. In addition, the separation process remains unaffected by the general impurities, demonstrating its true potential as an alternative sorbent for practical applications. Moving forward, the delicate crystal dynamics and promoted capability for molecular recognition provide a new route for the design of next-generation sieve materials.

Solid-solvent processing of ultrathin, highly loaded mixed-matrix membrane for gas separation.

Mixed-matrix membranes (MMMs) that combine processable polymer with more permeable and selective filler have potential for molecular separation, but it remains difficult to control their interfacial compatibility and achieve ultrathin selective layers during processing, particularly at high filler loading. We present a solid-solvent processing strategy to fabricate an ultrathin MMM (thickness less than 100 nanometers) with filler loading up to 80 volume %. We used polymer as a solid solvent to dissolve metal salts to form an ultrathin precursor layer, which immobilizes the metal salt and regulates its conversion to a metal-organic framework (MOF) and provides adhesion to the MOF in the matrix. The resultant membrane exhibits fast gas-sieving properties, with hydrogen permeance and/or hydrogen-carbon dioxide selectivity one to two orders of magnitude higher than that of state-of-the-art membranes.

Ultra-stable fully-aromatic microporous polyamide membrane for molecular sieving of nitrogen over volatile organic compound.

Microporous polymer membranes are promising candidates for industrial membrane-based gas separation because of their high separation performance. However, their relatively low stability due to the local rearrangement of polymer chains during usage remains a problem. Hence, we propose the construction of a fully aromatic polymer structure in a microporous polymer membrane to enhance membrane stability. Four triptycene-based microporous polyamides were synthesized via the polymerization of 2,6,14-triaminotriptycene with aromatic acyl chloride and/or aliphatic acyl chlorides. Their properties were characterized and compared by using nuclear magnetic resonance (NMR) and Brunauer-Emmett-Teller analyses. The synthesized polyamides were fabricated into composite membranes by employing a solution process; their stability was evaluated for the molecular sieving of nitrogen over volatile organic compounds such as cyclohexane. Low-field NMR and X-ray photoelectron spectroscopy were used to investigate the differences in the properties of membranes with different structures at different times. The results showed that the fully aromatic polyamide membrane made from 2,6,14-triaminotriptycene and aromatic acyl chloride displayed constant rejection (99 %) and nitrogen permeability (approximately 50 Barrer) for the molecular sieving of nitrogen over cyclohexane during 100-d experiments, indicating good stability. This approach paves the way for the industrialization of microporous polymer membranes from a theoretical perspective.

Ion-Conducting Ceramic Membrane Reactors for the Conversion of Chemicals.

Ion-conducting ceramic membranes, such as mixed oxygen ionic and electronic conducting (MIEC) membranes and mixed proton-electron conducting (MPEC) membranes, have the potential for absolute selectivity for specific gases at high temperatures. By utilizing these membranes in membrane reactors, it is possible to combine reaction and separation processes into one unit, leading to a reduction in by-product formation and enabling the use of thermal effects to achieve efficient and sustainable chemical production. As a result, membrane reactors show great promise in the production of various chemicals and fuels. This paper provides an overview of recent developments in dense ceramic catalytic membrane reactors and their potential for chemical production. This review covers different types of membrane reactors and their principles, advantages, disadvantages, and key issues. The paper also discusses the configuration and design of catalytic membrane reactors. Finally, the paper offers insights into the challenges of scaling up membrane reactors from experimental stages to practical applications.

Zeolites and metal-organic frameworks for gas separation: the possibility of translating adsorbents into membranes.

Zeolites and metal-organic frameworks (MOFs) represent an attractive class of crystalline porous materials that possesses regular pore structures. The inherent porosity of these materials has led to an increasing focus on gas separation applications, encompassing adsorption and membrane separation techniques. Here, a brief overview of the critical properties and fabrication approaches for zeolites and MOFs as adsorbents and membranes is given. The separation mechanisms, based on pore sizes and the chemical properties of nanochannels, are explored in depth, considering the distinct characteristics of adsorption and membrane separation. Recommendations for judicious selection and design of zeolites and MOFs for gas separation purposes are emphasized. By examining the similarities and differences between the roles of nanoporous materials as adsorbents and membranes, the feasibility of zeolites and MOFs from adsorption separation to membrane separation is discussed. With the rapid development of zeolites and MOFs towards adsorption and membrane separation, challenges and perspectives of this cutting-edge area are also addressed.

Zr-MOF membranes with ultra-fast water-selective permeation towards intensification of esterification reaction.

Well-intergrown polycrystalline UiO-66 membranes were successfully synthesized on a polymeric substrate under mild synthesis conditions of a lower temperature and short synthesis time. The resulted UiO-66 membranes with fast water selective transport channels exhibited unprecedentedly high solvent dehydration performance with a permeation flux of ∼6100 g m-2 h-1 and a separation factor of ∼7500, showing great potential for intensification of esterification reaction.

Formation and fine-tuning of metal-organic frameworks with carboxylic pincers for the recognition of a C2H2 tetramer and highly selective separation of C2H2/C2H4.

Highly efficient ethylene (C2H4) and acetylene (C2H2) separation is a great challenge and an important process in current industries. Herein, we finely tune a new family of 6-c metal-organic frameworks (MOFs) with crab-like carboxylic pincers for the recognition of a C2H2 tetramer and afford NTU-72 with high adsorption C2H2/C2H4 selectivity (56-441, 298 K) as well as unprecedented recovery of both highly pure C2H4 (99.95%) and C2H2 (99.36%). Furthermore, the effective binding of a C2H2 tetramer by NTU-72's carboxylic pincers has been revealed by gas-loaded crystallography and Raman spectral studies. Our work provides a novel approach for the selective binding of a small molecular cluster for designing high-performance MOFs.

Polycrystalline Metal-Organic Framework Membranes for Separation of Light Hydrocarbons.

Due to facile designability and versatile nanospace, metal-organic frameworks (MOFs) have been considered as promising membrane materials. Compared to the mixed matrix membranes that incorporated with MOF particles, the polycrystalline MOF membranes demonstrates significant advantages in maximum utilizing the crystalline nanospace, and thus yielding a fruitful of achievements in the last twenty years. Although some reviews have summarized the development of MOF-based membranes, the theoretical framework for oriented design and preparation of polycrystalline MOF membranes for highly efficient separation of light hydrocarbons remains in infancy. Herein, in this review, the fabrication strategies of polycrystalline MOF membranes and the corresponding performance in the separation of light hydrocarbons were classified and summarized. Particularly, the MOF membranes with global and local dynamics have been proposed as an interesting topic promoted performance.

Eliminating lattice defects in metal-organic framework molecular-sieving membranes.

Metal-organic framework (MOF) membranes are energy-efficient candidates for molecular separations, but it remains a considerable challenge to eliminate defects at the atomic scale. The enlargement of pores due to defects reduces the molecular-sieving performance in separations and hampers the wider application of MOF membranes, especially for liquid separations, owing to insufficient stability. Here we report the elimination of lattice defects in MOF membranes based on a high-probability theoretical coordination strategy that creates sufficient chemical potential to overcome the steric hindrance that occurs when completely connecting ligands to metal clusters. Lattice defect elimination is observed by real-space high-resolution transmission electron microscopy and studied with a mathematical model and density functional theory calculations. This leads to a family of high-connectivity MOF membranes that possess ångström-sized lattice apertures that realize high and stable separation performance for gases, water desalination and an organic solvent azeotrope. Our strategy could enable a platform for the regulation of nanoconfined molecular transport in MOF pores.

Aliquots of MIL-140 and Graphene in Smart PNIPAM Mixed Hydrogels: A Nanoenvironment for a More Eco-Friendly Treatment of NaCl and Humic Acid Mixtures by Membrane Distillation.

The problem of water scarcity is already serious and risks becoming dramatic in terms of human health as well as environmental safety. Recovery of freshwater by means of eco-friendly technologies is an urgent matter. Membrane distillation (MD) is an accredited green operation for water purification, but a viable and sustainable solution to the problem needs to be concerned with every step of the process, including managed amounts of materials, membrane fabrication procedures, and cleaning practices. Once it is established that MD technology is sustainable, a good strategy would also be concerned with the choice of managing low amounts of functional materials for membrane manufacturing. These materials are to be rearranged in interfaces so as to generate nanoenvironments wherein local events, conceived to be crucial for the success and sustainability of the separation, can take place without endangering the ecosystem. In this work, discrete and random supramolecular complexes based on smart poly(N-isopropyl acrylamide) (PNIPAM) mixed hydrogels with aliquots of ZrO(O2C-C10H6-CO2) (MIL-140) and graphene have been produced on a polyvinylidene fluoride (PVDF) sublayer and have been proven to enhance the performance of PVDF membranes for MD operations. Two-dimensional materials have been adhered to the membrane surface through combined wet solvent (WS) and layer-by-layer (LbL) spray deposition without requiring further subnanometer-scale size adjustment. The creation of a dual responsive nanoenvironment has enabled the cooperative events needed for water purification. According to the MD's rules, a permanent hydrophobic state of the hydrogels together with a great ability of 2D materials to assist water vapor diffusion through the membranes has been targeted. The chance to switch the density of charge at the membrane-aqueous solution interface has further allowed for the choice of greener and more efficient self-cleaning procedures with a full recovery of the permeation properties of the engineered membranes. The experimental evidence of this work confirms the suitability of the proposed approach to obtain distinct effects on a future production of reusable water from hypersaline streams under somewhat soft working conditions and in full respect to environmental sustainability.

Recent Progress on Nanomaterial-Facilitated Electrochemical Strategies for Cancer Diagnosis.

Cancer is a malignant disease that endangers human life, especially owing to its high fatality rate; therefore, rapid and accurate early screening is needed to effectively improve the survival rate. Compared with traditional cancer detection methods, electrochemical biosensors that recognize cancer biomarkers in blood have the advantages of low invasiveness, fast diagnosis, and low cost. However, there is always a trade-off between sensitivity and selectivity, which limits the detection of trace amounts of biomarkers produced in the early stages. To address this issue, an increasing number of nanomaterials with simultaneous improvements in both sensitivity and selectivity have recently been reported. In this review, different categories of state-of-the-art electrochemical biosensors and their operating principles are introduced, and their respective advantages and disadvantages are described. Furthermore, the review discusses the existing detection strategies and performance of nanomaterial-based cancer biosensors for biomarker recognition, providing overall guidance for the material selection of different biomarkers. Finally, the main challenges involving existing electrochemical cancer biosensors are evaluated to present the future development prospects of nanomaterials and detection strategies.

Deformation constraints of graphene oxide nanochannels under reverse osmosis.

Nanochannels in laminated graphene oxide nanosheets featuring confined mass transport have attracted interest in multiple research fields. The use of nanochannels for reverse osmosis is a prospect for developing next-generation synthetic water-treatment membranes. The robustness of nanochannels under high-pressure conditions is vital for effectively separating water and ions with sub-nanometer precision. Although several strategies have been developed to address this issue, the inconsistent response of nanochannels to external conditions used in membrane processes has rarely been investigated. In this study, we develop a robust interlayer channel by balancing the associated chemistry and confinement stability to exclude salt solutes. We build a series of membrane nanochannels with similar physical dimensions but different channel functionalities and reveal their divergent deformation behaviors under different conditions. The deformation constraint effectively endows the nanochannel with rapid deformation recovery and excellent ion exclusion performance under variable pressure conditions. This study can help understand the deformation behavior of two-dimensional nanochannels in pressure-driven membrane processes and develop strategies for the corresponding deformation constraints regarding the pore wall and interior.

Scalable Printing of Prussian Blue Analogue@Au Edge-Rich Microcubes as Flexible Biosensing Microchips Performing Ultrasensitive Sucrose Fermentation Monitoring.

Sucrose is one of the most applied carbon sources in the fermentation process, and it directly determines the microbial metabolism with its concentration fluctuation. Meanwhile, sucrose also plays a key role of a protective agent in the production of biological vaccines, especially in the new mRNA vaccines for curing COVID-19. However, rapid and precise detection of sucrose is always desired but unrealized in industrial fermentation and synthetic biology research. In order to address the above issue, we proposed an ultrasensitive biosensor microchip achieving accurate sucrose recognition within only 12 s, relying on the construction of a Prussian blue analogue@Au edge-rich (PBA@AuER) microarchitecture. This special geometric structure was formed through exactly inducing the oriented PBA crystallization toward a certain plane to create more regular and continuous edge features. This composite was further transformed to a screen-printed ink to directly and large-scale fabricate an enzymatic biosensor microchip showing ultrahigh sensitivity, a wide detection range, and a low detection limit to the accurate sucrose recognition. As confirmed in a real alcohol fermentation reaction, the as-prepared microchip enabled us to accurately detect the sucrose and glucose concentrations with outstanding reusability (more than 300 times) during the whole process through proposing a novel analytical strategy for the binary mixture substrate system.