Toward robust quantification of dopamine and serotonin in mixtures using nano-graphitic carbon sensors.

Monitoring the coordinated signaling of dopamine (DA) and serotonin (5-HT) is important for advancing our understanding of the brain. However, the co-detection and robust quantification of these signals at low concentrations is yet to be demonstrated. Here, we present the quantification of DA and 5-HT using nano-graphitic (NG) sensors together with fast-scan cyclic voltammetry (FSCV) employing an engineered N-shape potential waveform. Our method yields 6% error in quantifying DA and 5-HT analytes present in in vitro mixtures at concentrations below 100 nM. This advance is due to the electrochemical properties of NG sensors which, in combination with the engineered FSCV waveform, provided distinguishable cyclic voltammograms (CVs) for DA and 5-HT. We also demonstrate the generalizability of the prediction model across different NG sensors, which arises from the consistent voltammetric fingerprints produced by our NG sensors. Curiously, the proposed engineered waveform also improves the distinguishability of DA and 5-HT CVs obtained from traditional carbon fiber (CF) microelectrodes. Nevertheless, this improved distinguishability of CVs obtained from CF is inferior to that of NG sensors, arising from differences in the electrochemical properties of the sensor materials. Our findings demonstrate the potential of NG sensors and our proposed FSCV waveform for future brain studies.

Unraveling the complex electrochemistry of serotonin using engineered graphitic sensors.

Fast-scan cyclic voltammetry (FSCV) with micron-sized carbon sensors is a promising approach for monitoring the fast dynamics of serotonin (5-HT) neuromodulatory signals in the brain. However, sensor performance using FSCV can be compromised by complex chemical reactions associated with the reduction and oxidation of 5-HT, posing considerable challenges to detection of 5-HT in vivo. Herein we describe the use of engineered graphitic sensors to characterize the complex electrochemistry of 5-HT under a wide range of measurement conditions, with the aim of optimizing the FSCV conditions for in vivo quantitative 5-HT detection. These measurements reveal that water plays a significant role in driving side reactions during low-voltage FSCV measurements, leading to the observation of a well-defined secondary redox couple we associated with the redox reaction of tryptamine 4,5-dione. Remarkably, these side reactions can persist subsequent to the primary redox events associated with 5-HT. Furthermore, the results reveal a critical deviation from this ideal redox behavior if the FSCV anodic limit exceeds +0.8 V, which can be attributed to the generation of radical species from water oxidation. These new insights could lead to new FSCV protocols for more reliable 5-HT detection.

Mechanisms of Interface Cleaning in Heterostructures Made from Polymer-Contaminated Graphene.

Heterostructures obtained from layered assembly of 2D materials such as graphene and hexagonal boron nitride have potential in the development of new electronic devices. Whereas various materials techniques can now produce macroscopic scale graphene, the construction of similar size heterostructures with atomically clean interfaces is still unrealized. A primary barrier has been the inability to remove polymeric residues from the interfaces that arise between layers when fabricating heterostructures. Here, the interface cleaning problem of polymer-contaminated heterostructures is experimentally studied from an energy viewpoint. With this approach, it is established that the interface cleaning mechanism involves a combination of thermally activated polymer residue mobilization and their mechanical actuation. This framework allows a systematic approach for fabricating record large-area clean heterostructures from polymer-contaminated graphene. These heterostructures provide state-of-the-art electronic performance. This study opens new strategies for the scalable production of layered materials heterostructures.

Metal-Free Hydrosilylation Polymerization by Merging Photoredox and Hydrogen Atom Transfer Catalysis.

Organosilicon compounds and polymers have found wide applications as synthetic building blocks and functional materials. Hydrosilylation is a common strategy toward the synthesis of organosilicon compounds and polymers. Although transition-metal-catalyzed hydrosilylation has achieved great advances, the metal-free hydrosilylation polymerization of dienes and bis(silane)s, especially the one suitable for both electron-rich and electron-deficient dienes, is largely lacking. Herein, we report a visible-light-driven metal-free hydrosilylation polymerization of both electron-rich and electron-deficient dienes with bis(silane)s by using the organic photocatalyst and hydrogen atom transfer (HAT) catalyst. We achieved the well-controlled step-growth hydrosilylation polymerizations of the electron-rich diene and bis(silane) monomer due to the selective activation of Si-H bonds by the organic photocatalyst (4CzIPN) and the thiol polarity reversal reagent (HAT 1). For the electron-deficient dienes, hydrosilylation polymerization and self-polymerization occurred simultaneously in the presence of 4CzIPN and aceclidine (HAT 2), providing the opportunity to produce linear, hyperbranched, and network polymers by rationally tuning the concentration of electron-deficient dienes and the ratio of bis(silane)s and dienes to alter the proportion of the two polymerizations. A wide scope of bis(silane)s and dienes furnished polycarbosilanes with high molecular weight, excellent thermal stability, and tunable architectures.

Electrospun graphene oxide/MIL-101(Fe)/poly(acrylonitrile-co-maleic acid) nanofiber: A high-efficient and reusable integrated photocatalytic adsorbents for removal of dye pollutant from water samples.

The electrospun graphene oxide/MIL-101(Fe)/poly(acrylonitrile-co-maleic acid) nanofibers (E-spun GO/MIL-101(Fe)/PANCMA NFs) were fabricated by a facile electrospinning method and used as integrated photocatalytic adsorbents (IPAs) to remove dye pollutant from water samples. Compared with E-spun GO/PANCMA and E-spun MIL-101(Fe)/PANCMA NFs, the fabricated E-spun GO/MIL-101(Fe)/PANCMA NFs exhibited higher adsorption ability and excellent photocatalytic activity towards a model pollutant Rhodamine B (RhB). Under the optimized conditions, the as-prepared IPAs achieved almost complete adsorption of RhB within 15 min with the maximum adsorption capacity of 10.46 mg/g. Under visible-light irradiation, 93.7% of RhB in 20 mL water sample was degraded within 20 min, and the degradation kinetics of RhB fitted well with the first-order kinetic model. In addition, LC-MS analysis of the RhB degradation products confirmed the degradation pathways, and the generated •OH radicals played important roles in the degradation process. Importantly, the E-spun GO/MIL-101(Fe)/PANCMA NFs exhibited good reusability and could be reused for consecutive 20 cycles, which make them promising candidate materials in the field of industrial applications and environmental remediation.

Anomalous sensitivity enhancement of nano-graphitic electrochemical micro-sensors with reducing the operating voltage.

Microscopic interactions between electrochemical sensors and biomolecules critically influence the sensitivity. Here, we report an unexpected dependence of the sensitivity on the upper potential limit (UPL) in voltammetry experiments. In particular, we find that the sensitivity of substrate-supported nano-graphitic micro-sensors in response to dopamine increases almost linearly with the inverse of UPL in voltammetry experiments with rapid potential sweeps. Our experiments and multi-physics simulations reveal that the main cause behind this phenomenon is the UPL-induced electrostatic force that influences the steady-state number of dopamine molecules on the sensor surface. Our findings illustrate a new strategy for enhancing the performance of planar electrochemical micro-sensors.

Recent advances in separation applications of polymerized high internal phase emulsions.

Polymerized high internal phase emulsions as highly porous adsorption materials have received increasing attention and wide applications in separation science in recent years due to their remarkable merits such as highly interconnected porosity, high permeability, good thermal and chemical stability, and tailorable chemistry. In this review, we attempt to introduce some strategies to utilize polymerized high internal phase emulsions for separation science, and highlight the recent advances made in the applications of polymerized high internal phase emulsions for diverse separation of small organic molecules, carbon dioxide, metal ions, proteins, and other interesting targets. Potential challenges and future perspectives for polymerized high internal phase emulsion research in the field of separation science are also speculated at the end of this review.

An Electrochemical Biochip for Measuring Low Concentrations of Analytes With Adjustable Temporal Resolutions.

Electrochemical micro-sensors made of nano-graphitic (NG) carbon materials could offer high sensitivity and support voltammetry measurements at vastly different temporal resolutions. Here, we implement a configurable CMOS biochip for measuring low concentrations of bio-analytes by leveraging these advantageous features of NG micro-sensors. In particular, the core of the biochip is a discrete-time ∆Σ modulator, which can be configured for optimal power consumption according to the temporal resolution requirements of the sensing experiments while providing a required precision of ≈ 13 effective number of bits. We achieve this new functionality by developing a design methodology using the physical models of transistors, which allows the operating region of the modulator to be switched on-demand between weak and strong inversion. We show the application of this configurable biochip through in-vitro measurements of dopamine with concentrations as low as 50 nM and 200 nM at temporal resolutions of 100 ms and 10 s, respectively.

Spatial defects nanoengineering for bipolar conductivity in MoS2.

Understanding the atomistic origin of defects in two-dimensional transition metal dichalcogenides, their impact on the electronic properties, and how to control them is critical for future electronics and optoelectronics. Here, we demonstrate the integration of thermochemical scanning probe lithography (tc-SPL) with a flow-through reactive gas cell to achieve nanoscale control of defects in monolayer MoS2. The tc-SPL produced defects can present either p- or n-type doping on demand, depending on the used gasses, allowing the realization of field effect transistors, and p-n junctions with precise sub-µm spatial control, and a rectification ratio of over 104. Doping and defects formation are elucidated by means of X-Ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory. We find that p-type doping in HCl/H2O atmosphere is related to the rearrangement of sulfur atoms, and the formation of protruding covalent S-S bonds on the surface. Alternatively, local heating MoS2 in N2 produces n-character.

Nano-engineering the material structure of preferentially oriented nano-graphitic carbon for making high-performance electrochemical micro-sensors.

Direct synthesis of thin-film carbon nanomaterials on oxide-coated silicon substrates provides a viable pathway for building a dense array of miniaturized (micron-scale) electrochemical sensors with high performance. However, material synthesis generally involves many parameters, making material engineering based on trial and error highly inefficient. Here, we report a two-pronged strategy for producing engineered thin-film carbon nanomaterials that have a nano-graphitic structure. First, we introduce a variant of the metal-induced graphitization technique that generates micron-scale islands of nano-graphitic carbon materials directly on oxide-coated silicon substrates. A novel feature of our material synthesis is that, through substrate engineering, the orientation of graphitic planes within the film aligns preferentially with the silicon substrate. This feature allows us to use the Raman spectroscopy for quantifying structural properties of the sensor surface, where the electrochemical processes occur. Second, we find phenomenological models for predicting the amplitudes of the redox current and the sensor capacitance from the material structure, quantified by Raman. Our results indicate that the key to achieving high-performance micro-sensors from nano-graphitic carbon is to increase both the density of point defects and the size of the graphitic crystallites. Our study offers a viable strategy for building planar electrochemical micro-sensors with high-performance.

Versatile construction of van der Waals heterostructures using a dual-function polymeric film.

The proliferation of van der Waals (vdW) heterostructures formed by stacking layered materials can accelerate scientific and technological advances. Here, we report a strategy for constructing vdW heterostructures through the interface engineering of the exfoliation substrate using a sub-5 nm polymeric film. Our construction method has two main features that distinguish it from existing techniques. First is the consistency of its exfoliation process in increasing the yield and in producing large (>10,000 µm2) monolayer graphene. Second is the applicability of its layer transfer process to different layered materials without requiring a specialized stamp-a feature useful for generalizing the assembly process. We demonstrate vdW graphene devices with peak carrier mobility of 200,000 and 800,000 cm2 V-1 s-1 at room temperature and 9 K, respectively. The simplicity of our construction method and its versatility to different layered materials may open doors for automating the fabrication process of vdW heterostructures.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers for efficient adsorption and photocatalytic removal of malachite green and leucomalachite green.

Electrospun reduced graphene oxide/TiO2/poly(acrylonitrile-co-maleic acid) composite nanofibers (E-spun RGO/TiO2/PANCMA NFs) were fabricated using electrospinning of the dispersive solution of PANCMA, GO and TiO2 followed by post-chemical reduction. The obtained composite nanofibers were compressed in a dialyzer and then used to absorb and degrade malachite green (MG) and leucomalachite green (LMG) from aqueous solution. Compared to the E-spun TiO2/PANCMA and GO/TiO2/PANCMA NFs, the E-spun RGO/TiO2/PANCMA NFs exhibited higher adsorption capacity and photocatalytic degradation ability. Under optimized conditions, 90.6% of MG and 93.7% of LMG from 50 mL aqueous sample solution were adsorbed on the RGO/TiO2/PANMA NFs (3.0 mg fibers) in 2.0 min, and subsequent the 91.4% and 95.2% of MG and LMG adsorbed on the NFs were degradated in 60 min under UV irradiation, respectively. In addition, the E-spun RGO/TiO2/PANMA NFs exhibited good reusability and could be reused in multiple cycles of operations for adsorption and photocatalytic degradation of MG and LMG. This work demonstrated that the electrospun composite nanofibers are promising materials for removal of pollutants from environmental water samples.

Magnetic stir cake sorptive extraction of trace tetracycline antibiotics in food samples: preparation of metal-organic framework-embedded polyHIPE monolithic composites, validation and application.

In this work, a novel Fe3O4@Cu3(btc)2-embedded polymerized high internal phase emulsion (Fe3O4@HKUST-1-polyHIPE) monolithic cake was synthesized, characterized and used as an adsorbent in the magnetic stir cake sorptive extraction (MSCSE) and determination of tetracycline antibiotics (TCs) in food samples by a combination of with high-performance liquid chromatography-fluorescence detection (HPLC-FLD). The prepared Fe3O4@HKUST-1-polyHIPE monolithic composites displayed a strong extraction ability and high column capacity due to enhanced interactions such as π-π interactions, hydrogen bonding, and electrostatic interactions. The extraction and desorption conditions were evaluated, and the calibration curves of four spiked TCs were linear (R2 ≥ 0.9991) in the range from 20 to 800 ng mL-1 for milk and egg samples, and 20 to 800 ng g-1 for chicken muscle and kidney samples. The limits of detection and the limits of quantification of the four TCs by using the proposed MSCSE-HPLC-FLD method were in the range of 1.9-4.6 and 5.5-13.9 ng mL-1 for milk and egg samples, and 1.8-3.7 and 5.3-13.0 ng g-1 for chicken muscle and kidney samples, respectively. The recoveries of the target TCs from spiked food samples were in the range from 86.6 to 110.7% with relative standard deviations lower than 7.0%. The proposed method was successfully applied for the determination of these four TCs in milk, egg, chicken muscle, and kidney samples.

miR-126 promotes the growth and proliferation of leukemia stem cells by targeting DNA methyltransferase 1.

Previous studies have showed that the interaction between microRNAs (miRNAs) and leukemia stem cells (LSCs) may be a cause of drug resistance of acute myeloid leukemia (AML). However, whether miR-126 participates in the pathogenesis of AML remains unclear. In our study, we first examined the expression of miR-126 in CD34+ or CD34- cells isolated from blood samples and LSC cell line: KG-1a-LSCs and MOLM13-LSCs by qRT-PCR analysis. Then miR-126 inhibitor and mimics were applied to evaluate the roles of miR-126 in cell proliferation of LSC cell lines using CCK-8 assay and Ki-67 staining. Moreover, flow cytometry analysis was used to assess the apoptosis of LSC cell lines treated with miR-126 inhibitor of mimics. In addition, we analyzed the relationship between miR-126 and DNA methyltransferase 1 (DNMT1) by bioinformatics analysis and dual-luciferase reporter assay. Western blot analysis was applied to examine the protein expression level of DNMT1 in miR-126 mimics treated LSC cells. Results showed that miR-126 expression was significantly higher in CD34+ cells and KG-1a-LSCs and MOLM13-LSCs. Knockdown of miR-126 in KG-1a-LSCs and MOLM13-LSCs inhibited cell proliferation, and promoted apoptosis. miR-126 could regulate DNA methyltransferase 1 (DNMT1) expression by directly binding to it. In conclusion, these findings suggested that miR-126 may promote cell proliferation of LSCs by targeting DNMT1.

Development and evaluation of an experimental protocol for 3-D visualization and characterization of the structure of bacterial biofilms in porous media using laboratory X-ray tomography.

The development of a reliable model allowing accurate predictions of biofilm growth in porous media relies on a good knowledge of the temporal evolution of biofilm structure within the porous network. Since little is known about the real 3-D structure of biofilms in porous media, this work was aimed at developing a new experimental protocol to visualize the 3-D microstructure of the inside of a porous medium using laboratory X-ray microtomography. A reliable and reproducible methodology is proposed for (1) growing a biofilm inside a porous medium, and (2) X-ray tomography-based characterization of the temporal development of the biofilm at the inlet of the biofilter. The statistical analysis proposed here also validates the results presented in the literature based on a biofilm structure single measurement.