Green synthesis of N-rich carbon dot-derived crosslinked covalent organic nanomaterial for multipurpose chromatographic applications.

Carbon dots (CDs) derived crosslinked covalent organic nanomaterials (CONs) possessing high specific surface area and abundant surface functional groups are considered to be potential candidates for multimodal chromatographic separations. Typically, the synthesis of CDs and CONs requires harsh reaction conditions and toxic organic solvents, hence, the pursuit of facile and mild preparation strategies is the goal of researchers. In this work, 3-aminopropyltriethoxysilane and D-glucose were used as nitrogen and carbon sources, respectively, to prepare amino-CDs (AmCDs) by rapid low-temperature polymerization rather than the common high-temperature and high-pressure reaction. Then, surface functionalization of the aminated silica gel was carried out in a deep eutectic solvent by using hydrophilic AmCDs and 1,3,5-triformylbenzene (TFB) as the functional monomers. Consequently, a novel N-rich CDs derived CON surface-functionalized silica gel (AmCDs-CON@SiO2) was obtained under mild reaction conditions. The combination of AmCDs and TFB created an ideal CON based chromatographic stationary phase. The incorporation of TFB not only contributed to the successful construction of a crosslinked CON, but also enhanced the interaction forces. The developed AmCDs-CON@SiO2 has a great potential for versatile applications in liquid chromatography. This study proposes a simple stationary phase preparation strategy by the surface modification of silica gel with CDs-based CON. Moreover, this study verified the application potential of CDs derived CON in chromatographic separation. This not only promotes the development of CDs in the field of liquid chromatographic stationary phase, but also provides some reference value for the wide application of cross-linked CON.

Dispersive hierarchically porous composites based on defective MOFs as mixed-mode stationary phases for chromatographic separation.

Defective metal-organic frameworks-based composites with excellent separation properties were obtained. The mesoporous metal-organic frameworks were selected and deliberately designed to be deficient, and they were then combined with polyacrylamide to be modified on the surface of silica microspheres. The prepared composites were employed as mixed-mode stationary phase in chromatographic separation, and they were compared to both conventional microporous metal-organic framework-based columns and commercial columns. It showed improved selectivity and retention toward both hydrophilic and hydrophobic analytes, allowing for the effective separation of nine nucleosides and nucleobases, eight alkaloids, six antibiotics, and five alkylbenzenes. Additionally, the column was used to effectively separate the active ingredients in the daring substance of honeysuckle, revealing a wide range of possible applications. For the same batch of analytes, three batches of distinct materials demonstrated consistent separation effects. It also demonstrated excellent chromatographic repeatability and stability, with relative standard deviations of the retention time and/or column efficiency being found to be less than 0.8% and 0.9%, respectively. The dispersive hierarchically porous composites were demonstrated to be effective in chromatographic separation, and the results expanded the potential uses of defective MOFs with dispersed multi-level pores.

UPLC-Q-Exactive/MS based analysis explore the correlation between components variations and anti-influenza virus effect of four quantified extracts of Chaihu Guizhi decoction.

ETHNOPHARMACOLOGICAL RELEVANCE: Chaihu Guizhi decoction (CGD) is a classic Traditional Chinese Medicine (TCM) prescription for the treatment of influenza and fever, composes of Bupleuri Radix (Chaihu), Cinnamomi Ramulus (Guizhi), Scutellariae Radix (Huangqin), Codonopsis Radix (Dangshen), Glycyrrhizae Radix Et Rhizoma Praeparata Cum Melle (Zhigancao), Pinelliae Rhizoma Praeparatum (Fabanxia), Zingiberis Rhizoma Recens (Shengjiang), Paeoniae Radix Alba (Baishao) and Jujubae Fructus (Dazao) in the ratio of 12:4.5:4.5:4.5:3:6:4.5:4.5:4. The efficacy of TCM, if there are differences, depends on the different extraction methods and extracted components. AIM OF THE STUDY: This study was to evaluate the anti-influenza virus effect of CGD extracts with different extraction methods, analyze the components and explore their correlation. MATERIALS AND METHODS: CGD were prepared with four extraction methods respectively, the traditional decoction (TD), two steps alcohol-water extraction (AWE), alcohol reflux extraction (AE) and water reflux extraction (WE). Based on the influenza mouse model, the efficacy of anti-influenza virus in vivo of the four CGD extracts were evaluated with the therapeutic index of body weight, rectal temperature, lung index, thymus index and lung viral load of mice. The chemical components in four CGD extracts, and compounds absorbed in rats blood with prototypes or metabolites were identified by UPLC-Q-Exactive/MS. The partial least squares (PLS) method was used to explore the correlation between the components variation in CGD extracts and the comprehensive efficacy index. The potential effective components were further accessed by molecular docking. RESULTS: Comparing with the other three extracts, AWE has the best anti-influenza effect. It could ameliorate the symptoms caused by influenza virus infection in mice, increase body weight and rectal temperature, reduce the lung index and virus load in lung tissue. 129, 144, 140 and 129 components were identified from TD, AWE, AE, and WE respectively. The identified components were mainly including flavonoids, terpenoids, organic acids, phenylpropanoids, amino acids, nucleosides, phenols, alkaloids, etc. 43 prototypes and 49 metabolites of CGD were detected in rat plasma after oral administration. Seven components, cinnamaldehyde, wogonoside, baicalin, baicalein, gallic acid, oroxylinA-7-O-glucuronide and coumarin, showed significant correlation with anti-influenza effects, all of which had good binding activity with NA, IL-6, STAT3, AKT1, EGFR and TNF. CONCLUSION: Two steps alcohol-water extraction was optimal for CGD preparation. Cinnamaldehyde, wogonoside, oroxylinA-7-O-glucuronide, coumarin, gallic acid, baicalein and baicalin play a certain essential role in anti-influenza effects and may be taken as a potential maker compounds for quality evaluation of CGD.

In situanchoring of Fe3O4/CNTs hybrids on basalt fiber for efficient electromagnetic wave absorption.

The development of practical and efficient electromagnetic wave (EMW) absorbing materials is a challenging research problem. A mussel-inspired molecular structure regulation strategy using polydopamine to increase the roughness and functional groups of basalt fiber (BF) surface, which can improve the fiber interfacial adhesion. Herein, a novel BF-Fe3O4/CNTs heterostructure is synthesized through a dip-coating adsorption process. The three-dimensional network structure of Fe3O4/CNTs hybridin situanchored on the surface of BF, which endows the composite to have good intrinsic magnetic and dielectric properties. Modulation of EMW absorption performance by controlling the addition of CNTs, the minimum RL of BF-Fe3O4/7C reaches to -40.57 dB at a thickness of 1.5 mm with CNTs addition of 7%. The enhanced EMW absorption performance of BF-Fe3O4/7C heterostructure may be attributed to the synergistic effects of interfacial polarization between the hollow magnetic Fe3O4spheres and CNTs, conduction loss, magnetic resonance loss and multiple reflection/scattering inside the BF. This work provides a simple pathway to design EMW absorbing materials with good environmental stability.

TiO2@MOF-919(Fe-Cu) as a sorbent for the extraction of benzoylurea pesticides from irrigation water and fruit juices.

The TiO2@MOF-919(Fe-Cu) solid-phase extraction material was prepared by growing MOF-919(Fe-Cu) in situ on three-dimensional radial TiO2 microspheres by a simple solvothermal method. This combination drew on both the resources of good single dispersion and extraction rate, which made it a better extraction material. It was accompanied with high-performance liquid chromatography (SPE-HPLC) for the separation and determination of four benzoylurea pesticides (triflumuron, chlorbenzuron, teflubenzuron and diflubenzuron) in afforestation irrigation water and juice samples (grape, peach and apple juices). Under the optimal conditions, the linearity of the method ranged from 1 to 400 µg L-1 with a correlation coefficient (R2) ≥ 0.9994, while the detection limit was in the range of 0.40-0.56 µg L-1 for the four pesticides. The adopted material showed good reusability and can be used no less than 10 times. The intra-day and inter-day precision were in the range of 1.78-3.24% and 4.06-5.08%, respectively. The proposed method was then successfully applied for the detection of benzoylurea pesticides in the spiked samples with good recoveries (72.3-108.4%) and good precision (5.15%) due to π-π and hydrophobic interactions between the analytes and adsorbent. The results show that the composite had the potential to be used as a SPE adsorbent for the enrichment and extraction of benzene ring structures containing imide groups in actual samples.

Core-shell MOFs-based composites of defect-functionalized for mixed-mode chromatographic separation.

The micropores of the metal-organic frameworks (MOFs) endow with the advantages of size selectivity and large specific surface area, etc., but they limit their applications toward the control of diffusion and transport processes. Here, we report a strategy to prepare the hierarchical porous material, functional defect, which allows incorporation of L-Cysteine in the MOF by defect-loading. Silica microspheres were modified with these materials to form core-shell composites and used as mixed-mode stationary phases for chromatographic separations. Compared with the traditional MOFs-based stationary phase, it exhibited superior efficiency and selectivity for separation of various analytes and highlighted the role of defect of MOFs and function of L-Cysteine. In addition to the rapid separation of hydrophobic compounds, the stationary phase showed great potential in the separation of hydrophilic analytes, especially for separation of ten carbohydrates and eight sulfonamides. It showed excellent chromatographic reproducibility and stability, and the repeatability of preparation was investigated by relative standard deviations of retention time and/or column efficiency of objective compounds, which was among different batches less than 1.81%. This demonstration provided deep understanding of separation mechanism between MOF-based composites with functional defect and analytes, and stimulated the wide applications of such defective MOFs complexes in separations and analysis.

Fabrication of two-dimensional metal-organic framework nanosheets/PDA composites as mixed-mode stationary phase for chromatographic separation.

The synthesis of two-dimensional metal-organic frameworks (2D MOFs)/polymer core-shell composites is reported which were composed of polydopamine modified 2D Zr-1,3,5-(4-carboxylphenyl)-benzene (2D Zr-BTB) nanosheets and silica microspheres via a double-solvent approach. In this way, the composites were obtained under the condition of two solvents with different polarities to avoid agglomeration and uneven modification of most MOFs particles on the surface of the silica, existing inevitably in the one-pot method. Compared with the reported MOFs@silica composites adopting one-pot solvent method, the prepared composites exhibited significantly enhanced separation performance for sulfonamides, antibiotics, nucleosides, and polycyclic aromatic hydrocarbons compounds. Furthermore, the retention mechanisms were demonstrated by studying the relationships of chromatographic retention factors of tested analytes versus a variety of parameters under RPLC and HILIC modes, respectively. The superior chromatographic repeatability and stability were validated through the relative standard deviations of the retention time and/or column efficiency, which were found to be less than 0.8% and 0.9%, respectively. The material showed efficient separation ability for several types of compounds and provided another selectivity for preparing composites based on 2D MOFs nanosheets and other functional molecules.

An alternative strategy to construct uniform MOFs-Grafted silica core-shell composites as mixed-mode stationary phase for chromatography separation.

The preparation of the metal-organic frameworks (MOFs)@silica core-shell microspheres as the stationary phases mainly relied on the method of electrostatic interaction between the metal ions of MOFs and the silanol groups. Herein, the ligands of MOFs were preferentially modified to the surface of silica as connection points and seed crystals to connect or form the MOFs. In this way, the evenness of the MOFs particles on the silica surface was effectively improved, and the prepared composites possessed excellent reproducibility and stability, including acid-base stability. The relative standard deviation of the retention time for repeatability ranged from 0.1% to 0.26% and for stability retention time from 0.3% to 0.6%. Compared with commercial columns, the prepared stationary phase showed enhanced separation selectivity for separation of both hydrophilic and hydrophobic compounds containing alkaloids, nucleosides, antibiotics and alkylbenzenes, etc. The obtained column was used as a matrix for fast separation and analysis of antibiotics in actual samples. In short, the composites showed superior reproducibility, stability and satisfactory separation performance towards a variety of compounds in the studied conditions. It also provided another way to improve the evenness of MOFs particles on the surface of silica and enhance the stability of them under polar conditions.

A novel approach for the preparation of core-shell MOF/polymer composites as mixed-mode stationary phase.

The nickel organic framework capped with polyvinylpyrrolidone was prepared and synergistically immobilized onto porous silica surface as the mixed-mode stationary phase for high-performance liquid chromatography. Here, polyvinylpyrrolidone firstly was chosen as functional molecules to change morphology and size of the metal organic framework. The silica microspheres were then modified by them via a simple bonding method rather than in-situ growth method with the aid of electrostatic interaction commonly used before. The stationary phase showed flexible selectivity for separation of both hydrophilic and hydrophobic compounds, especially for hydrophilic compounds such as carbohydrates, alkaloids and sulfonamides etc. The chromatographic behaviors were evaluated by investigating various factors, and a typical mixed-mode retention feature of the column was observed. The composites could be prepared repetitively, and relative standard deviations of retention time of objective compounds among different batches were less than 1.75%. It also showed excellent chromatographic reproducibility, stability and potentiality for application in real samples. In short, the composites can be used for a feasible option for analysis of multiple compounds as the mixed-mode stationary phase and it provides a general approach for preparing MOFs-based composites by changing morphology and size of MOFs.

Design and evaluation of novel MOF-polymer core-shell composite as mixed-mode stationary phase for high performance liquid chromatography.

A general method was developed for preparing a metal-organic framework-polymer composite coated silica core-shell stationary phase. Silica microspheres were comodified with metal-organic framework and polyvinylpyrrolidone rather than the in situ method of silica modification by original metal-organic framework particles. Metal-organic framework particles and polyvinylpyrrolidone on silica surface were beneficial to suppress silanol activity and enhance composite material tolerance, as well as increasing the water compatibility of the original metal-organic framework-based stationary phases. The stationary phase exhibited superior hydrophilic and hydrophobic performance in terms of separation for various analytes including seven alkaloids, six sulfonamides, five antibiotics, and five polycyclic aromatic hydrocarbons. Moreover, the composite material also showed excellent stability with the relative standard deviation of the retention time of 0.4 to 0.7%. The separation performance with real samples proved that the column has good practical application potential. In summary, the poposed method provides a general way for preparing metal-organic framework-polymer composite material and changed the current status of original metal-organic framework particles modified silica as a single mode chromatographic stationary phase.

A new strategy for the preparation of core-shell MOF/Polymer composite material as the mixed-mode stationary phase for hydrophilic interaction/ reversed-phase chromatography.

A facile method for efficient synthesis of core-shell composite material was proposed. In this method, the silica microspheres were co-modified with metal organic framework (MOF-235) and polyethylene glycol polymer (PEG) and used as mixed-mode stationary phase (MOF-235@PEG@silica) for high-performance liquid chromatography. Elemental analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller etc. methods were used to investigate the properties of the core-shell composite material. The MOF-235@PEG@silica stationary phase showed flexible selectivity for the separation of both hydrophilic and hydrophobic compounds especially for the separation of nine alkaloids, which showed superior hydrophilic separation performance than previous MOF-based composite stationary phases. Some factors including the pH of buffer salt, the ratio of organic phase and water phase in the mobile phase have been investigated, suggesting that the chromatographic retention mechanism of the column was a mixed mode of hydrophilic and reversed phase. The composite material also showed excellent chromatographic repeatability with the RSDs of the retention time found to be 0.2%-0.6% (n = 10) and the standard addition test in the actual sample proved that it can be used for practical sample analysis. In short, it provided a general way for preparing MOFs-based composites as mixed-mode chromatographic stationary phases, and changed the current status of MOF-based composite materials as single mode chromatographic stationary phases.

2D metal-organic framework nanosheets-assembled core-shell composite material as stationary phase for hydrophilic interaction liquid chromatography.

The core-shell composites were first prepared by surface modification of silica spheres with two-dimensional MOF-FDM-23 nanosheets via a simple approach. The successful immobilization of 2D MOF-FDM-23 on the silica (2D MOF-FDM-23@silica) was confirmed by series of method including elemental analysis, X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR) transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and the Brunauer-Emmett-Teller (BET). The obtained material showed excellent separation performance for multiple polar compounds such as sulfonamides, alkaloids, antibiotic and amino acid compounds etc. In addition, it was found to be superior to most reported MOF-based stationary phases in terms of separation performance, preparative reproducibility and chromatographic stability. The reproducibility of material preparation was demonstrated by the difference in retention time of the same mixture on three batches of the material at different times. The relative standard deviation (RSD) of the retention time for preparation repeatability was found to range from 0.5% to 1.4%. In short, the core-shell composite material prepared by this method broadened the application of MOF-based composites as chromatography stationary phase, and significantly developed the field of 2D MOF nanosheets in chromatography.

An alternative approach for the preparation of a core-shell bimetallic central metal-organic framework as a hydrophilic interaction liquid chromatography stationary phase.

A new type of core-shell composite material was prepared and applied as a hydrophilic interaction liquid chromatography (HILIC) stationary phase. In this work, silica spheres were first modified with a bimetallic central metal-organic framework (ZnCoMOF) by a new strategy of static self-assembled in situ growth. This strategy was beneficial for increasing the electrostatic interaction between the MOF ligand and silica via introducing a sodium dodecylbenzenesulfonate (SDBS) group. The ZnCoMOF@silica stationary phase was characterized and evaluated in comparison with amino-modified and bare silica columns in terms of various polar analytes including eight nucleosides and nucleobases, seven carbohydrates, and multiple sulfonamides and antibiotics. The effects of organic solvent concentration, water content, the concentration of the salt and the pH of the buffer solution on the retention time were studied, which demonstrated the typical retention behavior of HILIC on the ZnCoMOF@silica column. Compared with most reported MOF-based stationary phases, the new composite material showed excellent hydrophilic properties and separation efficiency for various polar analytes. Moreover, the obtained stationary phase showed good reproducibility and stability. The relative standard deviation (RSD) of the retention time for repeatability was found to range from 0.1% to 0.6%, and the RSD of the retention time for stability was found to range from 0.3% to 0.7%. Furthermore, the column batch-to-batch reproducibility showed excellent preparation reproducibility, which few reported in most previous MOF@silica composite materials. This specific preparation method offers an easy and novel way to manipulate the amount of MOF particles on silica, which extends a universal way to produce various MOF@silica stationary phases by the method of static self-assembled in situ growth.

Near-Infrared Fluorescence Probe for Evaluating Acetylcholinesterase Activity in PC12 Cells and In Situ Tracing AChE Distribution in Zebrafish.

Acetylcholinesterase (AChE) plays crucial roles in numerous physiological processes such as cell differentiation, cell apoptosis, and nerve tissue developments. Hence, it is highly necessary to design a fluorescent probe for monitoring AChE activity in complex living organisms. In this work, a near-infrared (NIR) off-on probe (CyN) was developed for AChE detection. CyN was exactly synthesized by introducing an N,N-dimethyl carbamyl moiety to hemicyanine (CyOH). AChE can "light up" strong NIR fluorescence through a cleavage special ester bond and transform CyN into CyOH. Moreover, CyN was qualified for imaging the dynamic change of AChE activity in PC12 cells with retinoic acid or hypoxia stimulation. In particular, the probe has been successfully applied for in situ tracing the intact distribution of AChE in living zebrafish. The observations indicate that major occurrence sites of endogenic AChE on zebrafish are the yolk sac and neuromasts. Overall, CyN shows great potential for use in AChE-related physiological studies.

Mussel-Inspired Fabrication of SERS Swabs for Highly Sensitive and Conformal Rapid Detection of Thiram Bactericides.

As an important sort of dithiocarbamate bactericide, thiram has been widely used for fruits, vegetables and mature crops to control various fungal diseases; however, the thiram residues in the environment pose a serious threat to human health. In this work, silver nanoparticles (AgNPs) were grown in-situ on cotton swab (CS) surfaces, based on the mussel-inspired polydopamine (PDA) molecule and designed as highly sensitive surface-enhanced Raman scattering (SERS) swabs for the conformal rapid detection of bactericide residues. With this strategy, the obtained CS@PDA@AgNPs swabs demonstrated highly sensitive and reproducible Raman signals toward Nile blue A (NBA) probe molecules, and the detection limit was as low as 1.0 × 10-10 M. More critically, these CS@PDA@AgNPs swabs could be served as flexible SERS substrates for the conformal rapid detection of thiram bactericides from various fruit surfaces through a simple swabbing approach. The results showed that the detection limit of thiram residues from pear, grape and peach surfaces was approximately down to the level of 0.12 ng/cm2, 0.24 ng/cm2 and 0.15 ng/cm2 respectively, demonstrating a high sensitivity and excellent reliability toward dithiocarbamate bactericides. Not only could these SERS swabs significantly promote the collection efficiency of thiram residues from irregular shaped matrices, but they could also greatly enhance the analytical sensitivity and reliability, and would have great potential for the on-site detection of residual bactericides in the environment and in bioscience fields.

Mussel-inspired immobilization of silver nanoparticles toward sponge for rapid swabbing extraction and SERS detection of trace inorganic explosives.

It is fairly crucial to detect inorganic explosives through a sensitive and fast method in the field of public safety, nevertheless, the high non-volatility and stability characteristics severely confine their accurate on-site detection from a real-world surface. In this work, an efficient, simple and cost effective method was developed to fabricate uniform silver nanoparticles (AgNPs) immobilized on polyurethane (PU) sponge through the in-situ reduction of polydopamine (PDA) based on mussel-inspired surface chemistry, in virtue of a large quantities catechol and amine functional groups. The formed PU@PDA@Ag sponges exhibited high SERS sensitivity, uniformity and reproducibility to 4-Aminothiophenol (4-ATP) probe molecule, and the limit of detection was calculated to be about 0.02 nmol L-1. Moreover, these PU@PDA@Ag sponges could be served as excellent flexible SERS substrates to rapidly detect trace inorganic explosives with high collection efficiency via swabbing extraction. The detection limit for perchlorates (ClO4-), chlorates (ClO3-) and nitrates (NO3-) were approximately down to 0.13, 0.13 and 0.11 ng respectively. These flexible substrates not only could drastically increase the sample collection efficiency, but also enhance analytical sensitivity and reliability for inorganic explosive, and would have a great potential application in the future homeland security fields.

Solid-phase extraction of phenoxyacetic acid herbicides in complex samples with a zirconium(IV)-based metal-organic framework.

A zirconium(IV)-based metal-organic framework material (MOF-808) has been synthesized in a simple way and used for the extraction of phenoxyacetic acids in complex samples. The material has good thermal and chemical stability, large specific surface area (905.36 m²/g), and high pore size (22.18 Å). Besides, it contains a large amount of Zr-O groups, easy-to-form Zr-O-H bond with carboxyl groups of phenoxyacetic acids, and possesses biphenyl skeleton structure, easy to interact with compounds through π-π and hydrophobic interactions. These characteristics make the material very suitable for the extraction of certain compounds with a high extraction efficiency and excellent selectivity. The extraction conditions were optimized, and then an analytical method was successfully established and applied for analysis of actual samples. The solid-phase extraction method based on prepared material had a wide linear range of 0.2-250 µg/L and a low detection limit of 0.1-0.5 µg/L for four phenoxyacetic acid compounds including 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy) propionic acid, 4-chlorophenoxyacetic acid, and dicamba. The relative standard deviations of intra- and interday precision were 1.8-3.8 and 4.3-6.9%, and the recoveries after spiking were between 77.1 and 109.3%. The results showed that the material is a desired substituent for the extraction of compounds with benzene ring structure containing carboxyl groups.

In-Situ Grown Silver Nanoparticles on Nonwoven Fabrics Based on Mussel-Inspired Polydopamine for Highly Sensitive SERS Carbaryl Pesticides Detection.

The rapid sampling and efficient collection of target molecules from a real-world surface is fairly crucial for surface-enhanced Raman scattering (SERS) to detect trace pesticide residues in the environment and in agriculture fields. In this work, a versatile approach was exploited to fabricate a flexible SERS substrate for highly sensitive detection of carbaryl pesticides, using in-situ grown silver nanoparticles (AgNPs)on non-woven (NW) fabric surfaces based on mussel-inspired polydopamine (PDA) molecules. The obtained NW@PDA@AgNPs fabrics showed extremely sensitive and reproducible SERS signals toward crystal violet (CV) molecules, and the detection limit was as low as 1.0 × 10-12 M. More importantly, these NW@PDA@AgNPs fabrics could be directly utilized as flexible SERS substrates for the rapid extraction and detection of trace carbaryl pesticides from various fruit surfaces through a simple swabbing approach. It was identified that the detection limits of carbaryl residues from apple, orange, and banana surfaces were approximately decreased to 4.02 × 10-12, 6.04 × 10-12, and 5.03 × 10-12 g, respectively, demonstrating high sensitivity and superior reliability. These flexible substrates could not only drastically increase the collection efficiency from multifarious irregular-shaped matrices, but also greatly enhance analytical sensitivity and reliability for carbaryl pesticides. The fabricated flexible and multifunctional SERS substrates would have great potential to trace pesticide residue detection in the environment and bioscience fields.

Controllable assembly of a hierarchical multiscale architecture based on silver nanoparticle grids/nanowires for flexible organic solar cells.

In this work, an effective and facile strategy was developed to assemble a flexible hierarchical multiscale architecture by incorporating microscale silver nanoparticles (AgNPs) grids into random silver nanowires (AgNWs) networks combined with a room-temperature chemical sintering mechanism. The microscale AgNPs grids was fabricated by assemble AgNPs into a series of twin lines directly on a hydrophilic PET substrate based on coffee-ring effect with ink-jet printing technique. By regulating the assembly architecture, a flexible hierarchical multiscale conductor based on AgNPs grids/AgNWs was successfully fabricated and demonstrated a high transmittance of 87.5%, low sheet resistance of 16.5 Ω/sq and excellent mechanical flexibility. The hierarchical multiscale architecture was fairly favorable to efficiently collect free charges among the gaps in the AgNWs network, as well as to enhance the stability of conductivity by creating continuous conduction pathways. As an anode electrode in a flexible organic solar cell, the hierarchical multiscale AgNPs grids/AgNWs conductor demonstrated a more power photoelectric conversion efficiency, which was even superior to the corresponding properties of the ITO network at a similar transmittance. This simple, low-cost and nonlithographic solution-based approach would further enhance current fabrication approaches to create patterned microstructures, and have great potential to fabricate multifarious functional patterns in flexible electronic devices.