Highly Active Hydrogen-rich Photothermal Reverse Water Gas Shift Reaction on Ni/LaInO3 Perovskite Catalysts with Near-unity Selectivity.

Photo-assisted reverse water gas shift (RWGS) reaction is regarded green and promising in controlling the reaction gas ratio in Fischer Tropsch synthesis. But it is inclined to produce more byproducts in high H2 concentration condition. Herein, LaInO3 loaded with Ni-nanoparticles (Ni NPs) was designed to obtain an efficient photothermal RWGS reaction rate, where LaInO3 was enriched with oxygen vacancies to roundly adsorbing CO2 and the strong interaction with Ni NPs endowed the catalysts with powerful H2 activity. The optimized catalyst performed a large CO yield rate (1314 mmol gNi -1 h-1 ) and ≈100 % selectivity. In situ characterizations demonstrated a COOH* pathway of the reaction and photoinduced charge transfer process for reducing the RWGS reaction active energy. Our work provides valuable insights on the construction of catalysts concerning products selectivity and photoelectronic activating mechanism on CO2 hydrogenation.

Efficient Extraction and Determination of Carbamate Pesticides in Vegetables Based on a Covalent Organic Frameworks with Acylamide Sites.

It is an important challenge to effectively extract and determine pesticides in complex samples. Covalent organic frameworks (COFs) are burgeoning porous crystalline organic materials with good environmental resistance, thus demonstrating great potential as adsorbents in contaminants detection. In this work, we design and synthesize a novel COF-TpDB via 1,3,5-triformylphloroglucinol (Tp) and 4,4'-diaminobenzoylanilide (DB) as well as its packed cartridge for solid phase extraction (SPE) of carbamate pesticides. Simulation calculations showed H-bonding facilitates the adsorption interactions between the carbamate pesticides and TpDB. A method was developed by coupling TpDB as SPE sorbents with high performance liquid chromatography-ultraviolet (HPLC-UV) detection to determine trace carbamate pesticides in vegetables. The established method showed a wide linear range of 0.1-200 ng mL-1 and low limit of detections (0.005-0.05 ng mL-1) for four carbamate pesticides. The applicability of TpDB as adsorbent was investigated for determination of trace carbamate pesticides residue in vegetables with satisfactory recoveries of four carbamates in the range of 80.4-101.2%. The results demonstrated that the COF-TpDB offer great potential for efficient extraction of carbamate pesticides from complicate matrices.

[Preparation of molecularly imprinted polymers-functionalized silica nanoparticles for the separation and recognition of aristolochic acids].

Aristolochic acids (AAs), which is commonly found in Aristolochia and Asarum plants, has been widely used in several traditional medicine practices due to their anti-inflammatory, anti-malarial, and anti-hyperglycemic activities. Recently, researchers have found a “decisive link” between liver cancer and aristolochic acid after analyzing a large number of liver cancer samples around the world. Therefore, a highly sensitive and selective method is required for the analysis of AAs in traditional Chinese medicines (TCM). For the determination of AAs in TCM, pretreatment is indispensable because in actual TCM samples, AAs is present in trace amounts and the complex matrix exerts interference. In the past decades, molecularly imprinted polymers (MIPs) have attracted considerable attention as an alternative for the trace analysis in complicated matrices. In this study, MIP-coated SiO2 nanoparticles (SiO2@MIP NPs) was prepared for the determination of aristolochic acid by surface molecular imprinting using aristolochic acid Ⅰ (AAI ) as the template molecule, 2-vinylpyridine (VPY) as the functional monomer, and ethyleneglycol dimethacrylate (EGDMA) as the cross-linking agent. Core-shell-structure SiO2@MIP NPs were obtained by modifying vinyl groups on the surface of SiO2 NPs, coating MIPs films onto the silica surface via selective polymerization, and final extraction of template AAI and generation of the recognition site. To find a suitable functional monomer for the best imprinting effect, the interaction between the template and the functional monomers, including acrylic acid (AA), methyl acrylic acid (MAA), 2-vinyl pyridine (VPY), acrylamide (AM), and methylacrylamide (MAM) was investigated. Electrostatic interaction between AAI and VPY resulted in the maximum decrease in absorbance of AAI at 250 nm. Therefore, VPY was chosen for the preparation of MIP. The morphological and physical properties of the MIPs were characterized by transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis, and N2 adsorption and desorption surface analysis. TEM images showed that SiO2 NPs were monodispersed with diameter of about 200 nm. The clear core-shell structure of SiO2@MIP NPs was observed, and the thickness of MIPs coating was about 35 nm. The FT-IR spectra of SiO2 NPs, vinyl group modified SiO2 and SiO2@MIP NPs revealed that the vinyl group and organic MIP layer were successfully modified at SiO2 sequentially. The results of thermogravimetric analysis were consistent with the FT-IR data for different SiO2 NPs. The nitrogen gas adsorption-desorption experiments showed that SiO2@MIP NPs and non-imprinted polymer (SiO2@NIP NPs) have the same pore volumes, while the surface area and pore size of MIPs were slightly larger than those of NIPs. Therefore, the difference in adsorption between SiO2@MIP NPs and SiO2@NIP NPs resulted from the imprinted sites on the MIP surface, rather than the difference in their surface areas. The adsorption properties of SiO2@MIP NPs were demonstrated by kinetic, isothermal, and selective adsorption experiments. The results of these experiments displayed that SiO2@MIP NPs reached adsorption equilibrium within a short period (120 s) and possessed a much higher rebinding ability than SiO2@NIP NPs. To verify the selectivity of SiO2@MIP NPs for AAI, three structural analogues (viz. tanshinone ⅡA, 2-methoxy-5-nitrophenol, and benzoic acid) were selected. The results showed that the binding capacity of SiO2@MIP NPs was much higher than those of these analogues. SiO2@MIP NPs have high adsorption capacity (5.74 mg/g), high imprinting factor (4.9), good selectivity coefficient (2.3-6.6) towards the structural analogues. SiO2@MIP NPs was used as an adsorbent and combined with HPLC for the selective separation of AAI in TCM. The recoveries of Kebia trifoliate samples spiked with three levels of AAI (0.3, 0.5, and 1.0 μg/mL) ranged from 73% to 83%. The results suggested that the proposed SiO2@MIP NPs could be used for selective enrichment of AAI from real complex TCM samples.

Hydrophilic molecularly imprinted polymers functionalized magnetic carbon nanotubes for selective extraction of cyclic adenosine monophosphate from winter jujube.

In this work, a green strategy was developed to prepare molecularly imprinted polymers functionalized magnetic carbon nanotubes in aqueous phase under mild conditions for cyclic adenosine monophosphate. Thanks to water solubility of chitosan, a natural polysaccharide which is rich in amino and hydroxyl groups, provided the feasibility to synthesize the green molecularly imprinted polymers for water soluble template in aqueous media. Coupled with high-performance liquid chromatography, the method exhibited a short equilibrium time (6 min), high adsorption capacity (22.42 µg/mg), high magnetic susceptibility, and good selectivity to template molecule with the imprinting factor of 2.94. A good linearity in the range of 0.020-3.0 mg/mL for target was obtained with a correlation coefficient of 0.9998. The limit of detection (signal-to-noise ratio = 3) and limit of quantitation (signal-to-noise ratio = 10) of the magnetic solid phase extraction method for cyclic adenosine monophosphate were 5 and 15 ng/mg, respectively. And the practical application of chitosan-based molecularly imprinted polymers as adsorbent to isolate and determine cyclic adenosine monophosphate in real natural samples (winter jujube) was demonstrated.

Selective and sensitive determination of celastrol in traditional Chinese medicine based on molecularly imprinted polymers modified Mn-doped ZnS quantum dots optosensing materials.

In this work, we proposed a facile strategy to prepare molecularly imprinted polymers (MIPs) modified Mn-doped ZnS quantum dots (QDs) as optosensing materials via sol-gel polymerization for specific recognition of celastrol (Cel) in traditional Chinese medicine (TCM). Firstly, L-Cysteine (L-Cys) modified Mn-doped ZnS QDs (L-Cys@Mn-ZnS) was used as imprinting substrate. The amino and carboxyl groups on the surface of Mn-ZnS QDs can provide more binding sites for imprinting polymerization. Then, the fluorescent MIPs was synthesized in the presence of L-Cys@Mn-ZnS QDs, template celastrol, 3-aminopropyl triethoxysilane (APTES) and ammonium hydroxide in the ethanol-water (9/1, v/v) solution. The morphology and structure of the products were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffractometer (XRD) and X-ray photoelectron spectroscopy (XPS). The resulting MIPs functionalized Mn-doped ZnS QDs (denoted as MIPs@L-Cys@Mn-ZnS QDs) had higher imprinting factor of 14.19 and significant selectivity. The MIPs@L-Cys@Mn-ZnS QDs as fluorescent probe exhibited sensitive response to Cel in the linear range from 0.1 µM to 3.5 µM and the limit of detection was estimated to be 35.2 nM. The probe was also applied for the detection of Cel in traditional Chinese medicine with recovery ranged from 88.0%-105.0%. The results confirmed that MIPs@L-Cys@Mn-ZnS QDs could efficiently and specifically capture Cel from actual complex traditional Chinese medicine samples.

The hydrophilic boronic acid-poly(ethylene glycol) methyl ether methacrylate copolymer brushes functionalized magnetic carbon nanotubes for the selective enrichment of glycoproteins.

An efficient and selective glycoproteins enrichment platform is essential to glycoprotein biomarkers in early clinic diagnostics. In this work, the poly (ethylene glycol) methyl ether methacrylate (PEGMA) and 4-vinylphenylboronic acid (VPBA) copolymer brushes grafted magnetic carbon nanotubes composite MCNTs@p (PEGMA-co-VPBA) was prepared by surface-initiated atom transfer polymerization and applied for the selective enrichment of glycoproteins from the complex biological samples. The as-prepared MCNTs@p (PEGMA-co-VPBA) nanocomposite was characterized by Fourier transform-infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometry (VSM). The MCNTs@p (PEGMA-co-VPBA) can recognize and bind specifically for glycoproteins via strong boronate affinity and excellent hydrophilicity and shows a really low non-specificity adsorption capability for non-glycoproteins. The adsorption capacity of MCNTs@p (PEGMA-co-VPBA) towards glycoproteins transferrin (Trf), horseradish peroxidase (HRP), and non-glycoproteins cytochrome c (Cyt C), lysozyme (Lyz) is 253.3 mg g-1, 51.1 mg g-1, 13.9 mg g-1 and 14.5 mg g-1, respectively. Furthermore, MCNTs@p (PEGMA-co-VPBA) can be applied to extract glycoproteins directly from egg white samples. These results demonstrated that MCNTs@p (PEGMA-co-VPBA) could be a potential affinity adsorbent in glycoprotein enrichment.

Background-Free Imaging of a Viral Capsid Proteins Coated Anisotropic Nanoparticle on a Living Cell Membrane with Dark-Field Optical Microscopy.

Exploring the diffusion dynamics of a viral capsid proteins (VCP)-functionalized nanocarrier on a living cell membrane could provide much kinetic information for the better understanding of their biological functionality. Gold nanoparticles are an excellent core material of nanocarriers because of the good biocompatibility as well as versatile surface chemistry. However, due to the strong scattering background from subcellular organelles, it is a grand challenge to selectively image an individual nanocarrier on a living cell membrane. In this work, we demonstrated a convenient strategy to effectively screen the scattering background from living cells for single-particle imaging with a polarization-resolved dual-channel imaging module. By taking advantage of the polarization of anisotropic gold nanoparticles (gold nanorods, GNRs), the signals from cell components could be counteracted after subtracting the sequential images one by one, while those transiently rotating GNRs on the cell membrane still exist in the processed image. In contrast to the previously reported methods, this method does not require a complicated optical setup alignment and sophisticated digital image analysis process. According to the single-particle imaging results, the majority of VCP-GNRs were anchoring on the cell membrane with confined diffusion. Interestingly, on further inspection of the diffusion trajectories, the particles displayed anomalous confined diffusion with randomly distributed large walking steps during the whole track. Non-Gaussian step distribution was noted, indicating heterogeneous binding and desorption processes on the cell membrane. As a consequence of the robust background screening capability, this approach would find broad applications for single-particle imaging under a noisy environment, e.g., living cells.

Click Synthesis of Hydrophilic Maltose-Functionalized Iron Oxide Magnetic Nanoparticles Based on Dopamine Anchors for Highly Selective Enrichment of Glycopeptides.

The development of methods to isolate and enrich low-abundance glycopeptides from biological samples is crucial to glycoproteomics. Herein, we present an easy and one-step surface modification strategy to prepare hydrophilic maltose functionalized Fe3O4 nanoparticles (NPs). First, based on the chelation of the catechol ligand with iron atoms, azido-terminated dopamine (DA) derivative was assembled on the surface of magnetic Fe3O4 nanoparticles by sonication. Second, the hydrophilic maltose-functionalized Fe3O4 (Fe3O4-DA-Maltose) NPs were obtained via copper(I)-catalyzed azide-alkyne cycloaddition (click chemistry). The morphology, structure, and composition of Fe3O4-DA-Maltose NPs were investigated by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectrometer (XPS), and vibrating sample magnetometer (VSM). Meanwhile, hydrophilicity of the obtained NPs was evaluated by water contact angle measurement. The hydrophilic Fe3O4-DA-Maltose NPs were applied in isolation and enrichment of glycopeptides from horseradish peroxidase (HRP), immunoglobulin (IgG) digests. The MALDI-TOF mass spectrometric analysis indicated that the novel NPs exhibited high detection sensitivity in enrichment from HRP digests at concentration as low as 0.05 ng µL(-1), a large binding capacity up to 43 mg g(-1), and good recovery for glycopeptides enrichment (85-110%). Moreover, the Fe3O4-DA-Maltose NPs were applied to enrich glycopeptides from human renal mesangial cells (HRMC) for identification of N-glycosylation sites. Finally, we identified 115 different N-linked glycopeptides, representing 93 gene products and 124 glycosylation sites in HRMC.

Turn-on fluorescent sensing of glutathione S-transferase at near-infrared region based on FRET between gold nanoclusters and gold nanorods.

A fluorescence resonance energy transfer (FRET) method based on gold nanoclusters capped glutathione (AuNCs@GSH) and amine-terminated gold nanorods (AuNRs) is designed for turn-on and near-infrared region (NIR) sensing of glutathione S-transferase (GST). The absorption band of AuNRs is tuned carefully to maximize the spectra overlap and enhance the efficiency of FRET. The FRET from multiple AuNCs to single AuNR quenches about 70% fluorescence emission of AuNCs. After GST is added, the strong specific interaction of GSH-GST can replace the AuNCs@GSH from AuNRs, FRET based on electrostatic interaction between AuNCs@GSH and AuNRs is switched off. Thus, emission enhancement of AuNCs@GSH is observed. The fluorescent enhancement is linearly with the increasing GST concentration over the range of 2-100 nM GST and the limit of detection for GST is about 1.5 nM.

A piezoelectric quartz crystal sensor array self assembled calixarene bilayers for detection of volatile organic amine in gas.

P-tert-butylcalix[n]arenes (n=4, 6, 8, abbreviated as CA[4], CA[6], CA[8], respectively) were immobilized on the Au surface of the piezoelectric quartz crystal by the reaction between CA[n] and the acid chloride terminated mercaptoacetic acid (MAA) self assembled monolayers to form MAA/CA[n] bilayers. The sensing films were not only immobilized easily and reproducibly, but also used to improve the reversibility of the sensor signal. The response characteristics show the response of CA to organic amine attributes to specific interaction between CA[n] (host) and organic amines (guest). The frequency shifts of n-butylamine and iso-butylamine are much larger than tert-butylamine and diethylamine because of shape-selection and hydrogen bonding. Compared to CA[6] and CA[4], CA[8] has highest sensitivity to organic amine due to having more flexibility to accommodate guest molecules. A sensor array with three-layer back-propagation neural network was applied to detect the binary mixture of n-butylamine in the range of 7.14-142 mull(-1) and iso-butylamine in the range of 7.14-57 mull(-1). The optimum values of learning rate (0.15) and momentum term (0.8) were determined by experiment. The best epoch of training was 1098. The root mean square error of prediction was 1.69 (mull(-1)) for n-butylamine, and 1.42 (mull(-1)) for iso-butylamine.