Controllable Synthesis of Titanium Silicon Molecular Zeolite Nanosheet with Short b-Axis Thickness and Application in Oxidative Desulfurization.

Titanium silicon molecular zeolite (TS-1) plays an important role in catalytic reactions due to its unique nanostructure. The straight channel on TS-1 was parallel to the orientation of the short b-axis and directly exposed to the aperture of the 10-member ring with a diameter of 0.54 nm × 0.56 nm. This structure could effectively reduce the diffuse restriction of bulk organic compounds during the oxidative desulfurization process. As a kind of cationic polymer electrolyte, polydimethyldiallyl ammonium chloride (PDDA) contains continuous [C8H16N+Cl-] chain segments, in which the Cl- could function as an effective structure-directing agent in the synthesis of nanomaterials. The chain of PDDA could adequately interact with the [0 1 0] plane in the preparation process of zeolite, and then the TS-1 nanosheet with short b-axis thickness (6 nm) could be obtained. The pore structure of the TS-1 nanosheet is controlled by regulating the content of PDDA. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 physical adsorption analysis, infrared absorption spectrum and ultraviolet-visible spectrum were used to determine the TS-1. The thinner nanosheets exhibit excellent catalytic performance in oxidative desulfurization of dibenzothiophene (DBT), in which the removal rate could remain at 100% after three recycles. Here, the TS-1 nanosheet with short b-axis thickness has a promising future in catalytic reactions.

Fabrication and Application of Ag@SiO2/Au Core-Shell SERS Composite in Detecting Cu2+ in Water Environment.

A sensitive and simple method for detecting Cu2+ in the water source was proposed by using surface-enhanced Raman scattering spectroscopy (SERS) based on the Ag@SiO2/Au core-shell composite. The Ag@SiO2 SERS tag was synthesized by a simple approach, in which Ag nanoparticles were first embedded with Raman reporter PATP and next coated with a SiO2 shell. The Ag@SiO2 nanoparticles had strong stability even in a high-concentration salty solution, and there were no changes to their properties and appearance within one month. The Ag@SiO2/Au composite was fabricated through a controllable self-assemble process. L-cysteine was decorated on the surface of a functionalized Ag@SiO2/Au composite, as the amino and carboxyl groups of it can form coordinate covalent bond with Cu2+, which shows that the Ag@SiO2/Au composite labelled with L-cysteine has excellent performance for the detection of Cu2+ in aqueous media. In this study, the SERS detection of Cu2+ was carried out using Ag@SiO2 nanoparticles, and the limit of detection (LOD) as low as 0.1 mg/L was achieved.

Plasmonic filter paper for preconcentration, separation and SERS detection harmful chemicals in chili product by fluid flow.

We proposed a triple functional SERS substrate by immobilized Ag nanoparticles on the surface of filter paper. The high dense Ag nanoparticles were distributed on the SERS substrate via in-situ growth process. By optimizing the parameter in preparation process, the optimal filter paper SERS substrate was fabricated by using 30 mM of AgNO3 with 20 S growth time. Due to capillary-effect wicking of cellulose fiber, the paper SERS substrate provide simple, fast and pump-free function for transferring analyte onto sharp tip through development of fluid. The fluid flow also brings target concentrate effect within the tip area. Furthermore, the separation feasibility was obtained during the development process of fluid. The preconcentrated effects not only enhanced the SERS signal of analyte, but also improve the fluorescence visible effect. The filter paper SERS substrate was successfully used for separating, concentrating and detecting Sudan dye from chili product, the detection limit could achieve 10-6 M. This study developed a portable, cost-effective and eco-friendly SERS substrate for separating and detecting trace chemical in food.

Quantitative monitoring ofloxacin in beef by TLC-SERS combined with machine learning analysis.

Ofloxacin is one kind of quinolone antibiotic drugs, the abuse of ofloxacin in livestock and aquaculture may bring bacterial resistance and healthy problem of people. The illegally feeding cattle with ofloxacin will help it keep health, but the sedimentation of ofloxacin could bring problem in food safety. The accurate, simple and instant monitoring ofloxacin from beef by portable sensor was of vital issue in food quality. A simple and reliable method was proposed for instant and quantitative detecting ofloxacin in beef, in which the thin-layer chromatography (TLC) -surface-enhanced Raman scattering (SERS) spectroscopy was in tandem with machine learning analysis base one principal component analysis-back propagation neural network (PCA-BPNN). The TLC plate was composed with diatomite, that was function as the stationary phase to separate ofloxacin from beef. The real beef juice was directly casted onto the diatomite plate for separating and detecting. The directly monitor ofloxacin from beef was achieved and the sensitivity down to 0.01 ppm. The PCA-BPNN was used as reliable model for quantitative predict the concentration of ofloxacin, that shown superior accuracy compared with the traditional model. The results verify that the diatomite plate TLC-SERS combined with machine-learning analysis is an effective, simple and accurate technique for detecting and quantifying antibiotic drug in meat stuff to improve the food safety.

SETD7 promotes metastasis of triple-negative breast cancer by YY1 lysine methylation.

Breast cancer has gradually become the predominant cause for cancer-associated death in women. The metastatic dissemination and underlying mechanisms of triple-negative breast cancer (TNBC) are not sufficiently understood. (Su(var)3-9, enhancer of zeste, Trithorax) domain-containing protein 7 (SETD7) is vital for promoting the metastasis of TNBC, as demonstrated in this study. Clinical outcomes were significantly worse in primary metastatic TNBC with upregulated SETD7. Overexpression of SETD7 in vitro and in vivo promotes migration of TNBC cells. Two highly conserved lysine (K) residues K173 and K411 of Yin Yang 1 (YY1) are methylated by SETD7. Further, we found that SETD7-mediated K173 residue methylation protects YY1 from the ubiquitin-proteasome degradation. Mechanistically, it was found that the SETD7/YY1 axis regulates epithelial-mesenchymal transition (EMT) and tumor cell migration via the ERK/MAPK pathway in TNBC. The findings indicated that TNBC metastasis is driven by a novel pathway, which may be a promising target for advanced TNBC treatment.

Rapid, convenient, and ultrasensitive point-of-care sensing of histamine from fish: A Portable chromatographic platform based on derivatization reaction.

Food poisoning caused by histamine ingestion is one of the prevalent allergies associated with fish consumption in the world. Reliable detection of histamine from fish by a portable platform was of urgent importance to food safety. A portable technology for on-site monitoring of histamine in tuna was established through combined azo-derivatized thin-layer chromatography (TLC) with surface-enhanced Raman scattering (SERS) spectroscopy. The real tuna meat sample was directly applied onto the portable sensor for the separation of histamine and azo-derivatizing of histamine was reacted on the TLC plate. The colorless histamine was visualized by azo-derivatization after spraying Pauly reagent onto the diatomite TLC plate. The molecule information and concentration of the histamine was measured and calculated by SERS spectra. Diatomite TLC plate was capable of separating histamine with 1.32 × 10-7 M of Au colloid for the SERS enhancement. Accordingly, the limit of detection of histamine from mixture sample could achieve 2.8 × 10-4 ppm. These results indicated that the portable azo-derivatized TLC-SERS sensor not only visualizes the histamine but also improves the intensity of the Raman spectra. The azo-derivatized TLC-SERS sensor could be applied for rapid, convenient, and ultrasensitive point-of-care sensing of histamine in fish.

Preparation of SERS active filter paper for filtration and detection of pesticides residue from complex sample.

The selectivity is needed mostly in SERS sensing because analytes of interest are commonly present in a complex mixture containing particles and impurities, which hinder the interactions between the laser and analyte being detected. In this manuscript, we describe our efforts developing a simple and instant. method to prepare a filter paper SERS sensor. Colloidal Ag nanoparticles were immobilized on one side of filter paper via an in-situ growth method. The fabrication process of the sensor could be finished in several minutes, and no special facility needed. The filter paper SERS sensor demonstrated a spectra uniformity with a 7.0 % point-by-point signal deviation. And the filter function of the sensor could effectively filter out interferences from samples in 1 min, that allowing the direct detection of thiram in ketchup by SERS with detection limit of 93 ppb. Furthermore, we used a Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method to detect malachite green (MG) in soil with a sensitivity as low as 0.01 ppm without any sample pre-treatment or purification. A SERS filter paper may open a new avenue for rapid testing of food quality during manufacturing as well as fast detection of potential contaminants in a myriad of substrates.

Review of Thin-Layer Chromatography Tandem with Surface-Enhanced Raman Spectroscopy for Detection of Analytes in Mixture Samples.

In the real world, analytes usually exist in complex systems, and this makes direct detection by surface-enhanced Raman spectroscopy (SERS) difficult. Thin layer chromatography tandem with SERS (TLC-SERS) has many advantages in analysis such as separation effect, instant speed, simple process, and low cost. Therefore, the TLC-SERS has great potential for detecting analytes in mixtures without sample pretreatment. The review demonstrates TLC-SERS applications in diverse analytical relevant topics such as environmental pollutants, illegal additives, pesticide residues, toxic ingredients, biological molecules, and chemical substances. Important properties such as stationary phase, separation efficiency, and sensitivity are discussed. In addition, future perspectives for improving the efficiency of TLC-SERS in real sample detecting are outlined.

On-site detection of pyrene from mixture with ppb level sensitivity by plasmonic TLC-DSERS.

Polycyclic aromatic hydrocarbons are a kind of persistent organic pollutants, which bring harmful effects to the ecological environment and human health. Therefore, it is critical to identify PAHs. In this study, we developed a highly efficient device for on-site identification of pyrene in edible oil using high performance plasmonic thin layer chromatography (PTLC) and dynamic surface-enhanced Raman spectroscopy (DSERS). PAHs in the mixture sample were efficiently separated on the PTLC plate and visualized under UV light, in which the plasmonic feature of the stationary phase could enhance the fluorescence of PAH. Then DSERS measurement was developed on a portable Raman spectrometer. The smaller size of Au NPs in the stationary phase could provide a lower theoretical plate height and provide higher separation efficiency. The sensitivity of the PTLC-DSERS method is down to 0.1 ppb, that nearly 4 orders of magnitude higher than current TLC-SERS method. The results indicate that this PTLC-DSERS method has the potential for on-site and sensitive identification of pyrene in the mixture.

Facile Synthesis of Diatomite/ß-Cyclodextrin Composite and Application for the Adsorption of Diphenolic Acid from Wastewater.

Diphenolic acid (DPA) is a kind of endocrine-disrupting compound, which brings serious health problems to humans and animals. An eco-friendly and cost-effective adsorbent was prepared through a simple method, in which the ß-Cyclodextrin(ß-CD) was crosslinked onto the surface of diatomite (DA), the as-prepared DA/ß-CD composite showed higher adsorption efficiency for DPA than DA as the host-guest interaction between DPA and ß-CD. DA is a kind of biosilica with a hierarchical pore structure that provides enough surface area for the DA/ß-CD. The surface area and pore size of DA/ß-CD were investigated by nitrogen adsorption and desorption. The DA/ß-CD composite illustrated a good adsorption capability, and was used for removing DPA from wastewater. The adsorption ratio of DPA could achieve 38% with an adsorption amount of 9.6 mg g-1 under room temperature at pH = 6. The adsorption isotherm curves followed the Langmuir (R2 = 0.9867) and Freundlich (R2 = 0.9748) models. In addition, the regeneration rate of the DA/ß-CD was nearly at 80.32% after three cycles of regeneration. These results indicated that the DA/ß-CD has the potential for practical removal of the EDC contaminants from wastewater.

IRAK2-NF-κB signaling promotes glycolysis-dependent tumor growth in pancreatic cancer.

BACKGROUND: Metabolic reprogramming has emerged as a core hallmark of cancer, and cancer metabolism has long been equated with aerobic glycolysis. Moreover, hypoxia and the hypovascular tumor microenvironment (TME) are major hallmarks of pancreatic ductal adenocarcinoma (PDAC), in which glycolysis is imperative for tumor cell survival and proliferation. Here, we explored the impact of interleukin 1 receptor-associated kinase 2 (IRAK2) on the biological behavior of PDAC and investigated the underlying mechanism. METHODS: The expression pattern and clinical relevance of IRAK2 was determined in GEO, TCGA and Ren Ji datasets. Loss-of-function and gain-of-function studies were employed to investigate the cellular functions of IRAK2 in vitro and in vivo. Gene set enrichment analysis, Seahorse metabolic analysis, immunohistochemistry and Western blot were applied to reveal the underlying molecular mechanisms. RESULTS: We found that IRAK2 is highly expressed in PDAC patient samples and is related to a poor prognosis. IRAK2 knockdown led to a significant impairment of PDAC cell proliferation via an aberrant Warburg effect. Opposite results were obtained after exogenous IRAK2 overexpression. Mechanistically, we found that IRAK2 is critical for sustaining the activation of transcription factors such as those of the nuclear factor-κB (NF-κB) family, which have increasingly been recognized as crucial players in many steps of cancer initiation and progression. Treatment with maslinic acid (MA), a NF-κB inhibitor, markedly attenuated the aberrant oncological behavior of PDAC cells caused by IRAK2 overexpression. CONCLUSIONS: Our data reveal a role of IRAK2 in PDAC metabolic reprogramming. In addition, we obtained novel insights into how immune-related pathways affect PDAC progression and suggest that targeting IRAK2 may serve as a novel therapeutic approach for PDAC.

Preparation of Plasmonic Ag@PS Composite via Seed-Mediated In Situ Growth Method and Application in SERS.

The colloidal polystyrene (PS) was synthesized and decorated with silver nanoparticles (Ag NPs). The plasmonic Ag@PS nanocomposite was prepared by loading Ag NPs on PS microsphere through a seed-mediated in situ growth route. The property of Ag NPs deposited on the PS microsphere could be precisely controlled by adjusting the concentration of the chemicals used in the growth medium. The growth step is only limited by the diffusion of growing species in the growth media to the surface of the Ag seed. The Ag@PS prepared via the in situ growth method exhibited two advantages compared with the self-assembled PS/Ag. First, the high-density of Ag NPs were successfully deposited on the surface of PS as the electroless-deposited Ag seed process, which brings nearly three times SERS enhancement. Second, the rapid preparation process for in situ growth method (half an hour, 10 h for the self-assembled method). The PS/Ag could detect Nile blue A (NBA) down to 10-7 M by SERS. Furthermore, the plasmonic Ag@PS SERS substrate was used for pesticide identification. The on-site monitoring malachite green (MG) from fish was achieved by portable Raman spectrometer, and the limit of detection (LOD) was 0.02 ppm. The Ag@PS substrate has also shown capability for simultaneously sensing multiple pesticides by SERS.

Ultra-Sensitive, Rapid and On-Site Sensing Harmful Ingredients Used in Aquaculture with Magnetic Fluid SERS.

The integration of surface-enhanced Raman scattering (SERS) spectroscopy with magnetic fluid provides significant utility in point-of-care (POC) testing applications. Bifunctional magnetic-plasmonic composites have been widely employed as SERS substrates. In this study, a simple and cost-effective approach was developed to synthesize magnetic-plasmonic SERS substrates by decorating silver nanoparticles onto magnetic Fe3O4 nanoparticles (AgMNPs), which function both as SERS-active substrates and magnetic fluid particles. The strong magnetic responsivity from AgMNPs can isolate, concentrate, and detect target analytes from the irregular surface of fish skin rapidly. We fabricate a microfluid chip with three sample reservoirs that confine AgMNPs into ever smaller volumes under an applied magnetic field, which enhances the SERS signal and improves the detection limit by two orders of magnitude. The magnetic fluid POC sensor successfully detected malachite green from fish with excellent selectivity and high sensitivity down to the picomolar level. This work achieves a label-free, non-destructive optical sensing approach with promising potential for the detection of various harmful ingredients in food or the environment.

Layer-by-Layer Assembly of Polystyrene/Ag for a Highly Reproducible SERS Substrate and Its Use for the Detection of Food Contaminants.

Polystyrene (PS) spheres were prepared through an emulsifier-free emulsion polymerization method, in which the reaction time, ionic strength, concentrations of copolymer were studied in detail. The resulting PS microspheres and Ag nanoparticles were used to construct a surface enhanced Raman scattering (SERS) substrate by a layer-by-layer assembly method. A relatively uniform distribution of PS/Ag in the films was obtained, and the multilayer substrate presented excellent SERS reproducibility and a tunable enhancement effect. The SERS substrate was used for detecting harmful pesticides (malachite green and dimetridazole) in food samples, with a limit of detection as low as 3.5 ppb. The obtained plasmonic composite has a promising future in the field of SERS sensing.

Fabrication and Application of SERS-Active Cellulose Fibers Regenerated from Waste Resource.

The flexible SERS substrate were prepared base on regenerated cellulose fibers, in which the Au nanoparticles were controllably assembled on fiber through electrostatic interaction. The cellulose fiber was regenerated from waste paper through the dry-jet wet spinning method, an eco-friendly and convenient approach by using ionic liquid. The Au NPs could be controllably distributed on the surface of fiber by adjusting the conditions during the process of assembling. Finite-difference time-domain theoretical simulations verified the intense local electromagnetic fields of plasmonic composites. The flexible SERS fibers show excellent SERS sensitivity and adsorption capability. A typical Raman probe molecule, 4-Mercaptobenzoicacid (4-MBA), was used to verify the SERS cellulose fibers, the sensitivity could achieve to 10-9 M. The flexible SERS fibers were successfully used for identifying dimetridazole (DMZ) from aqueous solution. Furthermore, the flexible SERS fibers were used for detecting DMZ from the surface of fish by simply swabbing process. It is clear that the fabricated plasmonic composite can be applied for the identifying toxins and chemicals.

Surface-enhanced Raman scattering of flexible cotton fiber-Ag for rapid adsorption and detection of malachite green in fish.

The residual of malachite green (MG) in fish is one of the major food safety concerns for consumers. It is important to develop simple and instant analytical methods to identify MG residues in fish. We fabricated flexible cotton surface-enhanced Raman scattering substrate, which offers good flexibility, uniformity and excellent adsorption capability. The UV-vis DRS spectra, transmission electron microscopy and scanning electron elemental mapping images shown that the Ag NPs were closely packed on the surface of cotton fiber. The adsorption feature of cotton fiber could adsorb MG from solution and surface of fish. The Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method was used to adsorb MG in fish for SERS sensing. The limit of detection of MG in fish using this developed method was as low as 0.05 ppm. The QuEChERS-SERS analysis method exhibits the capability for multiplex detecting mixture of MG and Dimetridazole at different ratios (5 ppm, 1/400 and 1/4000) from fish. The results indicated that the cotton fiber-Ag composite was suitable employed as SERS substrate for simple and instant detecting trace contaminants in food.

Fabrication of plasmonic cotton gauze-Ag composite as versatile SERS substrate for detection of pesticides residue.

Plasmonic cotton gauze-Ag composite were fabricated through a simple, instant and cost-effective way, in which the Ag NPs were immobilized on the surface of cotton gauze through in-situ growth process. The in-situ growth of Ag NPs was started from electroless-immobilized Ag seeds on the surface of cotton fiber, which could form numerous hot spots for SERS compared with current method. The cotton gauze-Ag composite was employed as versatile substrate in surface-enhanced Raman scattering (SERS) spectroscopy. The plasmonic cotton gauze-Ag exhibited excellent uniformity, temporal stability and enhanced effect for SERS measurement. The detection limit of P-aminothiopheno (PATP) was 10-8 M. Furthermore, the plasmonic cotton gauze-Ag composite presented excellent flexibility and adsorption capability, which enable to adsorb and detect pesticide residue from irregular surface of cucumber directly by simple swabbing process, the detection limit could achieve 0.1 ppm. The cotton gauze-Ag composite also shown excellent selectivity is SERS sensing. The fabrication method could be simply extended to other cellulose compound, such as absorbent cotton, paper and even for natural fibers. This study proposed a new method for fabricating the cost-effective, eco-friendly and flexible SERS substrates.

Facile detection of carbendazim in food using TLC-SERS on diatomite thin layer chromatography.

This work aims to isolate and detect pesticide (carbendazim) residue in real food samples: orange juice and kale leaves. The combination of on-chip thin layer chromatography (TLC) and surface enhanced Raman scattering (SERS) spectroscopy was used for the separating and detecting of carbendazim (MBC) from the complex food sample. In order to achieve on-site detection of MBC from real food sample, the portable Raman spectrometer was coupled with TLC-SERS. The porous stationary phase composed of diatomite biosilica is beneficial for SERS enhancement and eluent migration. The experiments exhibited that the diatomite chip was suitable for TLC separation and has not shown SERS background and provided excellent separation efficiency, 10-8 M silver colloids were appropriate for the SERS measurement on TLC chip. The food sample was directly spotted onto the diatomite chip for TLC separation without any pretreatment. The separation and detection process were finished in less than 5 min, the mixture of pyrimethanil, pymetrozine and MBC could be distinguished simultaneously by TLC-SERS at one diatomite chip. The MBC in orange juice and kale were successfully detected, and a limit of detection (LOD) less than 2 ppm could be achieved.

Author Correction: PLGA-based dual targeted nanoparticles enhance miRNA transfection efficiency in hepatic carcinoma.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Preparation of multi-functional magnetic-plasmonic nanocomposite for adsorption and detection of thiram using SERS.

Magnetic materials have been widely used for constructing substrate in surface enhanced Raman scattering (SERS) sensing due to the magnetic responsibility. Here, we reported a facile and effective approach to construct multi-functional SERS substrate based on assembling Ag nanoparticles (NPs) on porous Fe microspheres. The porous Fe microspheres were prepared through hydrogen reduction of Fe2O3 NPs with porous structure, in which the size and morphology of Fe could be well controlled. The surface of Fe was grafted with amino group, and then decorated with Ag NPs. The surface area and pore size of Fe microsphere were characterized by nitrogen adsorption and desorption. The Fe@Ag nanocomposite illustrated a good SERS activity. Furthermore, this substrate could be used for pesticide monitoring by portable Raman spectrometer. Especially, the porous Fe microsphere could adsorb analyte from target sample and the Fe@Ag could be concentrated by magnetic force to amplify the SERS signal for thiram detection.