MoS2 Hollow Multishelled Nanospheres Doped Fe Single Atoms Capable of Fast Phase Transformation for Fast-charging Na-ion Batteries.

Low Na+ and electron diffusion kinetics severely restrain the rate capability of MoS2 as anode for sodium-ion batteries (SIBs). Slow phase transitions between 2H and 1T, and from NaxMoS2 to Mo and Na2S as well as the volume change during cycling, induce a poor cycling stability. Herein, an original Fe single atom doped MoS2 hollow multishelled structure (HoMS) is designed for the first time to address the above challenges. The Fe single atom in MoS2 promotes the electron transfer, companying with shortened charge diffusion path from unique HoMS, thereby achieving excellent rate capability. The strong adsorption with Na+ and self-catalysis of Fe single atom facilitates the reversible conversion between 2H and 1T, and from NaxMoS2 to Mo and Na2S. Moreover, the buffering effect of HoMS on volume change during cycling improves the cyclic stability. Consequently, the Fe single atom doped MoS2 quadruple-shelled sphere exhibits a high specific capacity of 213.3 mAh g-1 at an ultrahigh current density of 30 A g-1, which is superior to previously-reported results. Even at 5 A g-1, 259.4 mAh g-1 (83.68 %) was reserved after 500 cycles. Such elaborate catalytic site decorated HoMS is also promising to realize other "fast-charging" high-energy-density rechargeable batteries.

Convolutional Neural Network-Driven Impedance Flow Cytometry for Accurate Bacterial Differentiation.

Impedance flow cytometry (IFC) has been demonstrated to be an efficient tool for label-free bacterial investigation to obtain the electrical properties in real time. However, the accurate differentiation of different species of bacteria by IFC technology remains a challenge owing to the insignificant differences in data. Here, we developed a convolutional neural networks (ConvNet) deep learning approach to enhance the accuracy and efficiency of the IFC toward distinguishing various species of bacteria. First, more than 1 million sets of impedance data (comprising 42 characteristic features for each set) of various groups of bacteria were trained by the ConvNet model. To improve the efficiency for data analysis, the Spearman correlation coefficient and the mean decrease accuracy of the random forest algorithm were introduced to eliminate feature interaction and extract the opacity of impedance related to the bacterial wall and membrane structure as the predominant features in bacterial differentiation. Moreover, the 25 optimized features were selected with differentiation accuracies of >96% for three groups of bacteria (bacilli, cocci, and vibrio) and >95% for two species of bacilli (Escherichia coli and Salmonella enteritidis), compared to machine learning algorithms (complex tree, linear discriminant, and K-nearest neighbor algorithms) with a maximum accuracy of 76.4%. Furthermore, bacterial differentiation was achieved on spiked samples of different species with different mixing ratios. The proposed ConvNet deep learning-assisted data analysis method of IFC exhibits advantages in analyzing a huge number of data sets with capacity for extracting predominant features within multicomponent information and will bring about progress and advances in the fields of both biosensing and data analysis.

Inorganic-Organic Nanoarchitectonics: MXene/Covalent Organic Framework Heterostructure for Superior Microextraction.

One of the difficulties limiting covalent organic frameworks (COFs) from becoming excellent adsorbents is their stacking/aggregation architectures owing to poor morphology/structure control during the synthesis process. Herein, an inorganic-organic nanoarchitectonics strategy to synthesize the MXene/COF heterostructure (Ti3 C2 Tx /TAPT-TFP) is developed by the assembly of ß-ketoenamine-linked COF on the Ti3 C2 Tx MXene nanosheets. The as-prepared Ti3 C2 Tx /TAPT-TFP retains the 2D architecture and high adsorption capacity of MXenes as well as large specific surface area and hierarchical porous structure of COFs. As a proof of concept, the potential of Ti3 C2 Tx /TAPT-TFP for solid-phase microextraction (SPME) of trace organochlorine pesticides (OCPs) is investigated. The Ti3 C2 Tx /TAPT-TFP based SPME method achieves low limits of detection (0.036-0.126 ng g-1 ), wide linearity ranges (0.12-20.0 ng g-1 ), and acceptable repeatabilities for preconcentrating trace OCPs from fruit and vegetable samples. This study offers insights into the potential of constructing COF or MXene-based heterostructures for the microextraction of environmental pollutants.

Green construction of magnetic azo porous organic polymer for highly efficient enrichment and detection of phenolic endocrine disruptors.

Porous organic polymers (POPs) are prominent sorbents for effective extraction of endocrine disrupting chemicals (EDCs). However, green and sustainable construction of functional POPs is still challenging. Herein, we developed a magnetic azo POP (Mazo-POP) for the first time using hydroxy-rich natural kaempferol and low-toxic basic fuchsin as monomers through a diazo coupling reaction. The Mazo-POP exhibited excellent extraction capabilities for EDCs with a phenolic structure. Consequently, it was used as a magnetic sorbent for extracting phenolic EDCs from water and fish samples, followed by ultrahigh-performance liquid chromatography-tandem mass spectrometric detection. The Mazo-POP based analytical method afforded a good linearity of 0.06-100 ng mL-1 and 0.3-500 ng g-1 for water and fish samples respectively, with detection limits (S/N = 3) of 0.02-0.5 ng mL-1 and 0.1-1.5 ng g-1, respectively. The method recovery was from 85.2% to 109% and relative standard deviation was less 5.3%. Moreover, the effective adsorption was mainly contributed by hydrogen bond, π-π interaction, pore filling and hydrophobic interaction. This work not only provides an efficient method for sensitive determination of phenolic EDCs, but also highlights the significance of green preparation of environmentally friendly sorbents for enriching/adsorbing pollutants.

Surface Crystal Modification of Na3 V2 (PO4 )3 to Cast Intermediate Na2 V2 (PO4 )3 Phase toward High-Rate Sodium Storage.

The two-phase reaction of Na3 V2 (PO4 )3 - Na1 V2 (PO4 )3 in Na3 V2 (PO4 )3 (NVP) is hindered by low electronic and ionic conductivity. To address this problem, a surface-N-doped NVP encapsulating by N-doped carbon nanocage (N-NVP/N-CN) is rationally constructed, wherein the nitrogen is doped in both the surface crystal structure of NVP and carbon layer. The surface crystal modification decreases the energy barrier of Na+ diffusion from bulk to electrolyte, enhances intrinsic electronic conductivity, and releases lattice stress. Meanwhile, the porous architecture provides more active sites for redox reactions and shortens the diffusion path of ion. Furthermore, the new interphase of Na2 V2 (PO4 )3 is detected by in situ XRD and clarified by density functional theory (DFT) calculation with a lower energy barrier during the fast reversible electrochemical three-phase reaction of Na3 V2 (PO4 )3 - Na2 V2 (PO4 )3 - Na1 V2 (PO4 )3 . Therefore, as cathode of sodium-ion battery, the N-NVP/N-CN exhibited specific capacities of 119.7 and 75.3 mAh g-1 at 1 C and even 200 C. Amazingly, high capacities of 89.0, 86.2, and 84.6 mAh g-1 are achieved after overlong 10000 cycles at 20, 40, and 50 C, respectively. This approach provides a new idea for surface crystal modification to cast intermediate Na2 V2 (PO4 )3 phase for achieving excellent cycling stability and rate capability.

Preparation of black phosphorus nanosheets/ zeolitic imidazolate framework nanocomposite for high-performance solid-phase microextraction of organophosphorus pesticides.

Design and preparation of new fiber coatings for solid-phase microextraction (SPME) is of significance to the sample preparation techniques. Herein, a facile strategy has been developed for the integration of the black phosphorus (BP) nanosheets with metal-organic framework (ZIF-8) to generate a BP/ZIF-8 nanocomposite. For the first time, the newly-synthesized BP/ZIF-8 nanocomposite was adopted as the SPME fiber coating for the extraction of organophosphorus pesticides (OPPs). Under the optimized conditions, the BP/ZIF-8 based SPME method gained acceptable linearity (0.04-20 µg L-1), low limits of detection (0.012-0.051 µg L-1) and good repeatability (3.2-8.1%). Coupled with gas chromatography-mass spectrometric detection, the developed SPME method was successfully used for the preconcentration of OPPs from environmental waters with the method recoveries from 92.0%-103.8%. This method offers a good alternative for the analysis of trace OPPs in environmental water samples.

Unlocking Enhanced Capacitive Deionization of NaTi2(PO4)3/Carbon Materials by the Yolk-Shell Design.

The low salt adsorption capacities (SACs) of benchmark carbon materials (usually below 20 mg g-1) are one of the most challenging issues limiting further commercial development of capacitive deionization (CDI), an energetically favorable method for sustainable water desalination. Sodium superionic conductor (NASICON)-structured NaTi2(PO4)3 (NTP) materials, especially used in combination with carbon to prepare NTP/C materials, provide emerging options for higher CDI performance but face the problems of poor cycling stability and dissolution of active materials. In this study, we report the development of the yolk-shell nanoarchitecture of NASICON-structured NTP/C materials (denoted as ys-NTP@C) using a metal-organic framework@covalent organic polymer (MOF@COP) as a sacrificial template and space-confined nanoreactor. As expected, ys-NTP@C exhibits good CDI performance, including exemplary SACs with a maximum SAC of 124.72 mg g-1 at 1.8 V in the constant-voltage mode and 202.76 mg g-1 at 100 mA g-1 in the constant-current mode, and good cycling stability without obvious performance degradation or energy consumption increase over 100 cycles. Furthermore, X-ray diffraction used to study CDI cycling clearly exhibits the good structural stability of ys-NTP@C during repeated ion intercalation/deintercalation processes, and the finite element simulation shows why yolk-shell nanostructures exhibit better performance than other materials. This study provides a new synthetic paradigm for preparing yolk-shell structured materials from MOF@COP and highlights the potential use of yolk-shell nanoarchitectures for electrochemical desalination.

Tunable nanochannel resistive pulse sensing device using a novel multi-module self-assembly.

Nanochannel-based resistive pulse sensing (nano-RPS) system is widely used for the high-sensitive measurement and characterization of nanoscale biological particles and biomolecules due to its high surface to volume ratio. However, the geometric dimensions and surface properties of nanochannel are usually fixed, which limit the detections within particular ranges or types of nanoparticles. In order to improve the flexibility of nano-RPS system, it is of great significance to develop nanochannels with tunable dimensions and surface properties. In this work, we proposed a novel multi-module self-assembly (MS) strategy which allows to shrink the geometric dimensions and tune surface properties of the nanochannels simultaneously. The MS-tuned nano-RPS device exhibits an enhanced signal-to-noise ratio (SNR) for nanoparticle detections after shrunk the geometric dimensions by MS strategy. Meanwhile, by tuning the surface charge, an enhanced resolution for viral particles detection was achieved with the MS-tuned nano-RPS devices by analyzing the variation of pulse width due the tuned surface charge. The proposed MS strategy is versatile for various types of surface materials and can be potentially applied for nanoscale surface reconfiguration in various nanofluidic devices.

Review of the Application of Raman Spectroscopy in Qualitative and Quantitative Analysis of Drug Polymorphism.

Drug polymorphism is an important factor affecting the drugs quality and clinical efficacy. Therefore, great attention should be paid to the crystal analysis of drugs with their researching and evaluating part. With the booming development of Raman spectroscopy in recent years, more and more crystal analysis investigations were based on vibrational spectroscopy. This review mainly discussed the qualitative and quantitative analysis of active pharmaceutical ingredients (API) and pharmaceutical preparation with Raman spectroscopy. On basis of the determination of the vibration mode of drug molecules and the analysis of their chemical structure, this method had the advantages of universal, non-destructive, fast determination, low samples and cost, etc. This review provides theoretical and technical support for crystal structure, which are worth popularizing. It is expected that it will be helpful to relevant government management institutions, pharmaceutical scientific research institutions and pharmaceutical manufacturers.

A hydrophilic-lipophilic triazine based hyper-crosslinked polymer for efficient enrichment of nitrobenzene compounds.

Sensitive, accurate, and simultaneous determination of nitrobenzene compounds (NBs) in environmental water samples is of great significance due to their high risk to human health. In this work, a new triazine-based hyper-crosslinked polymer named CC-Py was constructed via the Friedel-Crafts reaction between cyanuric chloride (CC), pyridine (Py) and 1,2-dichloroethane. Due to its excellent stability, high surface area and hydrophilic-lipophilic (amphiphilic) structure, the CC-Py exhibited a high affinity toward the NBs (nitrobenzene, 2-nitrotoluene, 2,6-dimethylnitrobenzene, 3-nitrotoluene, 4-nitrotoluene, 3-nitrochlorobenzene, 4-nitrochlorobenzene, 2-nitrochlorobenzene, 2,4-dimethylnitrobenzene, 3-nitrobromobenzene, 4-nitrobromobenzene and 4-nitroiodobenzene). Then, a CC-Py based solid-phase microextraction coupled with gas chromatography-flame ionization detection was developed to detect the twelve NBs in real water samples. The results showed that the method had low limits of detection (0.20-0.50 µg L-1), good reproducibility (relative standard deviations (RSDs) < 8.6%) and high enrichment factors (967-1590). The recoveries for the NBs in six different types of water samples were between 90% and 111% with the RSDs less than 7.5%. This work provides a facile and sensitive method for the determination of trace level of NBs in real water samples.

Functional Characterization and Phenotyping of Protoplasts on a Microfluidics-Based Flow Cytometry.

A better understanding of the phenotypic heterogeneity of protoplasts requires a comprehensive analysis of the morphological and metabolic characteristics of many individual cells. In this study, we developed a microfluidic flow cytometry with fluorescence sensor for functional characterization and phenotyping of protoplasts to allow an unbiased assessment of the influence of environmental factors at the single cell level. First, based on the measurement of intracellular homeostasis of reactive oxygen species (ROS) with a DCFH-DA dye, the effects of various external stress factors such as H2O2, temperature, ultraviolet (UV) light, and cadmium ions on intracellular ROS accumulation in Arabidopsis mesophyll protoplasts were quantitatively investigated. Second, a faster and stronger oxidative burst was observed in Petunia protoplasts isolated from white petals than in those isolated from purple petals, demonstrating the photoprotective role of anthocyanins. Third, using mutants with different endogenous auxin, we demonstrated the beneficial effect of auxin during the process of primary cell wall regeneration. Moreover, UV-B irradiation has a similar accelerating effect by increasing the intracellular auxin level, as shown by double fluorescence channels. In summary, our work has revealed previously underappreciated phenotypic variability within a protoplast population and demonstrated the advantages of a microfluidic flow cytometry for assessing the in vivo dynamics of plant metabolic and physiological indices at the single-cell level.

Covalent triazine-based frameworks for efficient solid-phase microextraction of phthalic acid esters from food-contacted plastics.

Owing to various health threats associated with phthalic acid esters (PAEs), this category of endocrine-disrupting compounds has attracted more and more public scrutiny. However, the efficient preconcentration of PAEs from complex food-contacted plastics still remains challenging. Herein, three covalent triazine-based frameworks (CTFs) were constructed by facile Friedel-Crafts reactions of cyanuric chloride (CC), with triptycene (TPC), fluorene (FL) and 1,3,5-triphenylbenzene (TPB), respectively. Three CTFs were then employed as solid-phase microextraction (SPME) coatings for the extraction of PAEs. Benefiting from the large surface area and high pore volume, the newly-synthesized CC-TPC based SPME method exhibited large enrichment factors (978-2210), low limits of detection (0.027-0.10 ng g - 1), satisfactory linear ranges (0.09-20 ng g - 1), acceptable repeatabilities (4.3-9.6%) and high relative recoveries (92.0-104.6%).

Sustainable synthesis of hydroxyl-functional porous organic framework as novel adsorbent for effective removal of organic micropollutants from water.

Organic micropollutants (OMPs) in water resources are a growing threat to aquatic ecosystems and human health. Efficient removal of polar OMPs is very challenging because of their high hydrophility. Synthesizing novel adsorbent capable of high-efficiently removing hydrophilic and hydrophobic micropollutants is highly desirable for water remediation. Here, using natural proanthocyanidin as building units, a novel hydroxyl-functional porous organic framework (denoted as PC-POF) with amphiphilic feature was synthesized through facile azo coupling reaction. Five sulfonamide antibiotics were selected as model OMPs for adsorption study. Adsorption experiments demonstrated a more rapid and efficient sulfonamides capture ability of the PC-POF than that of the most reported adsorbents due to strong hydrogen bonding, π stacking and electrostatic interactions. The PC-POF can be easily recovered and reused at least 5 times without obvious decline in adsorption performance. Moreover, experiments conducted at environmentally relevant concentrations (µg L-1) further confirmed a notable adsorption performance of the PC-POF even when the sulfonamides solution was rapidly passed through the PC-POF packed column. The PC-POF also showed good adsorption performance for other micropollutants like neonicotinoid insecticides, nitroimidazole antibiotics and triazine herbicides, indicating a promising prospect. This work provides a new strategy to construct amphiphilic adsorbent by using renewable resources for pollutants removal.

A novel porphyrin-based conjugated microporous nanomaterial for solid-phase microextraction of phthalate esters residues in children's food.

A novel porphyrin-based conjugated microporous polymer (PCMP) with microporous structure and nitrogen-rich pyrrole building blocks was synthesized. The PCMP was used as a coating material to prepare solid-phase microextraction (SPME) fibers by sol-gel technique. Due to the toxicity of the phthalate esters (PAEs) and the necessity for their sensitive determinations in some food samples, the SPME fiber was investigated for the extraction of eleven PAEs from six different children's milk beverages prior to their detection by gas chromatography-mass spectrometry. Under the optimal conditions, the linear response range for the PAEs was in the range from 0.03 to 200 µg L-1 and the limits of detection (S/N = 3) for the analytes were 0.01-3.00 µg L-1. The method recoveries for the PAEs were between 80% and 120%, with the relative standard deviations varying from 1.3% to 9.8%. The method was successfully applied for the determination of PAEs in children's milk beverages.

Heterointerface optimization in a covalent organic framework-on-MXene for high-performance capacitive deionization of oxygenated saline water.

Capacitive deionization (CDI) provides a promising option for affordable freshwater while simultaneously storing energy, but its large-scale application is usually limited owing to the poor performance of conventional materials in natural (oxygenated) saline water. Herein, we report heterointerface optimization in a covalent organic framework (COF)-on-MXene heterostructure achieving a high CDI performance for desalination of oxygenated saline water. The 2D heterostructure with the optimal core-shell architecture inherits the high conductivity and reversible ion intercalation/deintercalation ability of MXene, and the hierarchical porous structure, large porosity, and extraordinary redox capacity of COFs. Thanks to the heterointerface optimization, the MXene@COF heterostructure exhibits a very stable cycling performance over 100 CDI cycles with a maximum NaCl adsorption capacity of 53.1 mg g-1 in oxygenated saline water, among the state-of-the-art values for CDI electrodes and also exceeding those of most MXene-based or 2D materials. This study highlights the importance of heterointerface optimization in MXene-organic 2D heterostructures to promote CDI of natural (oxygenated) saline water.

Novel N-riched covalent organic framework for solid-phase microextraction of organochlorine pesticides in vegetable and fruit samples.

A covalent organic framework named N-COF was successfully constructed by the aldehyde-amine condensation reaction between 2,4,6-tris (4-formyl phenoxy)-1,3,5-triazine and 1,3-bis(4-aminophenyl) urea for the first time. The prepared N-COF exhibited good stability and high affinity to organochlorine pesticides (OCPs). Thus, the N-COF was served as solid phase microextraction fiber coating for extraction of six OCPs from vegetables and fruits including romaine lettuce, cabbage, Chinese cabbage, apple, pear and peach, followed by quantitation with gas chromatography-electron capture detector (GC-ECD). Under the optimal conditions, good linearities for the OCPs existed in the ranges from 0.1 to 1.0 ng g-1 to 100.0 ng g-1 for the samples. The low limits of detection for analytes were obtained in the range of 0.03-0.3 ng g-1. The present work can offer new alternative for sensitive analysis of trace level of OCPs in vegetables and fruits.

Efficient solid-phase microextraction of twelve halogens-containing environmental hormones from fruits and vegetables by triazine-based conjugated microporous polymer coating.

A triazine-based conjugated microporous polymer (TCMP) was generated by introduced 1, 3, 5-triazine into conjugated microporous polymer network via Friedel-Crafts reaction. Under the optimum synthesis conditions, the obtained TCMP has a loose and porous structure. It was then used as a fiber coating material for solid-phase microextraction (SPME) of halogens-containing environmental hormones. It showed a strong adsorption capability due to the halogen bond, electrostatic, π-π stacking and hydrophobicity interactions. An analytical method combining the TCMP coated fiber-based SPME with gas chromatography-electron capture detection was developed to determine twelve halogens-containing environmental hormones in vegetable and fruit samples. A wide linear range (0.07-100.0 ng g-1) with the determination coefficients in the range of 0.9907-0.9996 and low limits of detection (0.02-0.04 ng g-1, S/N = 3) were achieved under optimized experimental conditions. The applicability of the established method was evaluated by the determination of the environmental hormones from three different fruit samples (apple, nectarine and pear) and five vegetable samples (Chinese cabbage, pakchoi, baby cabbage, rape and round lettuce). The resulting relative recoveries ranged from 76.6% to 123% with the relative standard deviations less than 10%. This research demonstrates the application potential of the TCMP coated fiber in the analysis of the halogens-containing environmental hormones in real vegetable and fruit samples.

Deep Learning Assisted Microfluidic Impedance Flow Cytometry for Label-free Foodborne Bacteria Analysis and Classification.

According to the urgent need for rapid detection and identification of foodborne bacteria to prevent public health event, a microfluidic electrical impedance flow cytometry assisted with convolutional neural network (ConvNet) based deep learning algorithm was proposed in this study to analyze the impedance signals of bacteria. With the assistance of the deep learning algorithm, Escherichia coli (EPEC), Salmonella enteritidis (SE) and Vibrio parahaemolyticus (VP) were identified with an accuracy of 100%. The proposed impedance based analysis system can be potentially applied for pre-classification of different subtypes of bacteria in a label-free manner.Clinical Relevance-The whole platform can be miniaturized and applied for point-of-care testing (POCT) of pathogenic bacteria detection.

[Advances in construction of triazine-based porous organic polymers and their applications in solid phase microextraction].

The large surface area, adjustable pore structure, good thermal and chemical stabilities, and abundant π-electron systems make triazine-based porous organic polymers (TPOPs) as promising porous materials for gas storage, catalysis, energy conversion and adsorption. Recently, TPOPs have aroused ever-increasing interest and are considered as one of the research highlights in solid phase microextraction (SPME) and other sample pretreatment techniques. This minireview summarizes the recent advancements in the synthesis of TPOPs and their applications in SPME. The application prospects of the TPOPs in SPME and other sample pretreatment techniques are also presented.

Triazine-based covalent organic polymer: A promising coating for solid-phase microextraction.

Advancement of novel coating materials for solid-phase microextraction is highly needed for sample pretreatment. Herein, a triazine-based covalent organic polymer was constructed from the monomers of cyanuric chloride and trans-stilbene via the Friedel-Crafts reaction and thereafter used as a solid-phase microextraction fiber coating for the extraction of polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives. The newly-developed solid-phase microextraction method coupled with gas chromatography/flame ionization detection gives enhancement factors of 548-1236 and limits of detection of 0.40-2.81 ng/L for the determination of polycyclic aromatic hydrocarbons and their derivatives. The one fiber precision for five replicate determinations of the analytes and the fiber-to-fiber precision with three parallel prepared fibers, expressed as relative standard deviations, was in the range of 4.6-9.4% and 6.2-10.9%, respectively. The relative recoveries of the analytes for environmental water samples were in the range of 88.6-106.4% with the relative standard deviations ranging from 4.0 to 11.7% (n = 5).