Contractile Hairpin DNA-Mediated Dual-Mode Strategy for Simultaneous Quantification of Lactoferrin and Iron Ion by Surface-Enhanced Raman Scattering and Fluorescence Analysis.

DNA-mediated self-assembly technology with good sensitivity and affinity ability has been rapidly developed in the field of probe sensing. The efficient and accurate quantification of lactoferrin (Lac) and iron ions (Fe3+) in human serum and milk samples by the probe sensing method can provide useful clues for human health and early diagnosis of anemia. In this paper, contractile hairpin DNA-mediated dual-mode probes of Fe3O4/Ag-ZIF8/graphitic quantum dot (Fe3O4/Ag-ZIF8/GQD) NPs were prepared to realize the simultaneous quantification of Lac by surface-enhanced Raman scattering (SERS) and Fe3+ by fluorescence (FL). In the presence of targets, these dual-mode probes would be triggered by the recognition of aptamer and release GQDs to produce FL response. Meanwhile, the complementary DNA began to shrink and form a new hairpin structure on the surface of Fe3O4/Ag, which produced hot spots and generated a good SERS response. Thus, the proposed dual-mode analytical strategy possessed excellent selectivity, sensitivity, and accuracy due to the dual-mode switchable signals from "off" to "on" in SERS mode and from "on" to "off" in FL mode. Under the optimized conditions, a good linear range was obtained in the range of 0.5-100.0 µg/L for Lac and 0.01-5.0 µmol/L for Fe3+ and with detection limits of 0.14 µg/L and 3.8 nmol/L, respectively. Finally, the contractile hairpin DNA-mediated SERS-FL dual-mode probes were successfully applied in the simultaneous quantification of iron ion and Lac in human serum and milk samples.

A natural selenium polysaccharide from Pleurotus ostreatus: Structural elucidation, anti-gastric cancer and anti-colon cancer activity in vitro.

The development and application of new natural selenium polysaccharides with relatively clear structure and excellent activity have become hot and difficult issues. This study used GC-MS and 2D NMR to characterize the detailed chain structure information of selenium polysaccharide (Se-POP-3) from Selenium-enriched Pleurotus ostreatus, and then explored its anti-gastric cancer and anti-colon cancer effects in vitro. Results showed that the main chain of Se-POP-3 was →[3)-ß-D-Glcp-(1]2 â†’ 6)-ß-D-Glcp-(1 â†’ 3,6)-ß-D-Glcp-(1 â†’ 3)-ß-D-Glcp-(1→, and the branch was α-D-Glcp-(1 â†’ [4)-α-D-Glcp-(1]4→, which was connected to the main chain through the O-3 bond of →3,6)-ß-D-Glcp-(1 â†’ glycosidic bond. In addition, Se-POP-3 could reduce viability, induce apoptosis, inhibit migration and invasion, destroy the Bax/Bcl-2 ratio, and inhibit the epithelial-to-mesenchymal transition of MGC-803 and HCT-116 cells in vitro. Moreover, this study also showed that within the concentration range set in this study, Se-POP-3 had no significant effect on the growth of normal cells (NCM460 cells). This study can provide a theoretical basis for the potential application of Se-POP-3 as an anti-gastrointestinal cancer drug or functional food.

Capsule-like molecular imprinted polymer nanoparticles for targeted and chemophotothermal synergistic cancer therapy.

Selective cancer cell targeting, controlled drug release, easy construction and multiple therapeutic modalities are some of the desirable characteristics of drug delivery systems. We designed and built simple capsule-like molecular imprinted polymer (MIP)-based nanoparticles for targeted and chemo-photothermal synergistic cancer therapy. Using dopamine (DA) as functional monomer, cross-linking agent as well as photo-thermal agent, ZIF-8 (zeoliticimidazolate framework-8) as drug carrier, epitope of EGFR (epidermal growth factor receptor) as template molecules, molecular imprinted polymer (MIP) drug carrier was constructed. The ability of MIP layer to bind to EGFR epitope endowed the MD (DOX@MIP) particles to recognize EGFR-overexpressing cancer cells, while the pH-responsiveness and photothermal conversion ability of PDA (polydopamine) achieved chemo-photothermal synergistic effects upon NIR irradiation. Taken together, the MD nanoparticles integrated cancer cell targeting recognition, intelligent drug release, biocompatibility and chemo-photothermal effects, and is therefore a promising tool for targeted cancer therapy with minimal toxicity to normal cells, as well as tumor imaging.

A water-soluble selenium-enriched polysaccharide produced by Pleurotus ostreatus: Purification, characterization, antioxidant and antitumor activities in vitro.

The development and application of new selenium-enriched polysaccharides has become a critical topic in recent years. In this study, a natural selenium-enriched polysaccharide fraction (Se-POP-21) produced by Pleurotus ostreatus was purified, characterized, and investigated the antioxidant and antitumor activities in vitro. The Se-POP-21 was mainly composed of mannose, glucose, galactose and arabinose, with a molar ratio of 18.01:2.40:26.15:7.34, of which molecular weight was 15,888 Da and the selenium content was 5.31 µg/g. Spectral analysis demonstrated that Se-POP-21 represented a non-triple helix pyranopolysaccharide and selenium occurred in the form of C-O-Se and SeO. Molecular size and morphology studies showed that Se-POP-21 exhibited a spherical shape with a particle size distribution between 100 and 200 nm, even though Se-POP-21 aggregates were also found with a size between 500 and 600 nm. In addition, Se-POP-21 showed strong scavenging capacity to DPPH and hydroxyl radical. More, cell experiments showed that Se-POP-21 could reduce viability of A549, SKOV3, HepG2 and MCF-7 cells, induce apoptosis and inhibit metastasis of A549 cells. A potential mechanism was that Se-POP-21 inhibited the epithelial-to-mesenchymal transition of cancer cells. Se-POP-21 featured no significant effect on normal cells. Se-POP-21 showed great potential to develop into a natural antioxidant or low-toxic antitumor drug.

Physicochemical characterization and antitumor activity in vitro of a selenium polysaccharide from Pleurotus ostreatus.

Selenium-enriched polysaccharides have been gaining great attention for their antitumor activity in recent years. In this study, a novel selenium polysaccharide fraction (Se-POP-3) produced by Pleurotus ostreatus was characterized and its antitumor activity explored at cellular level. Results showed that Se-POP-3 has 25.9 µg/g of selenium, an average molecular weight of 16,106 Da, and is mainly composed of mannose, glucose and galactose with a molar ratio of 1.7:49.6:2.4. Spectra analysis revealed Se-POP-3 as a pyranopolysaccharide linked by α-glycoside bonds in the main chain, and selenium may occur in the form of COSe and SeO. A single sphere of Se-POP-3 has 50-60 nm in aqueous solution, even though it can agglomerate to form larger spherical structures. In vitro experiments with cancer and normal cell lines showed that Se-POP-3 can induce apoptosis and inhibit migration of cancer cells. Potential anticancer mechanism is that Se-POP-3 can disrupt the Bax/Bcl-2 protein ratio and inhibit the epithelial-to-mesenchymal transition (EMT) in cancer cells. Se-POP-3 showed no significant effect on the growth of normal cell lines. Se-POP-3 showed great potential as a broad-spectrum antitumor agent and dietary supplement.

Synthesis of tunable DNA-directed trepang-like Au nanocrystals for imaging application.

Multi-branched metal nanomaterials can exhibit precisely controllable plasmonic properties with the precise control of their sizes and morphologies. In this study, trepang-like gold nanocrystals (AuNCs) with tunable plasmonic properties were synthesized via DNA-directed self-assembly technology. The gold precursor was precisely controlled to be reduced and grow along the DNA skeleton of DNA-conjugated gold nanorods to form multi-branched trepang-like nanocrystals. It was investigated in detail and proven that several key factors greatly influenced the precise control of the morphology and plasmonic property of the proposed AuNCs during their synthesis, including the gold precursor, reducing agent, surfactant, loading amount of DNA and DNA structure. The relative finite-difference time-domain calculation results suggested that the change in the plasmonic resonance peak is consistent with the precise change in the size and morphology of the as-synthesized AuNCs. The trepang-like AuNCs exhibited broad absorption bands in the wavelength range of 700-1100 nm with a high photothermal conversion efficiency of 36.2%. Finally, the trepang-like AuNCs with good biocompatibility were applied in photothermal therapy and imaging analysis.

Preparation of novel alumina nanowire solid-phase microextraction fiber coating for ultra-selective determination of volatile esters and alcohols from complicated food samples.

A novel alumina nanowire (ANW) solid-phase microextraction (SPME) fiber coating was prepared by a simple and rapid anodization-chemical etching method for ultra-selective determination of volatile esters and alcohols from complicated food samples. Preparation conditions for ANW SPME fiber coating including corrosion solution concentration and corrosion time were optimized in detail for better surface morphology and higher surface area based on scanning electron microscope (SEM). Under the optimum conditions, homogeneous alumina nanowire structure of ANW SPME fiber coating was achieved with the average thickness of 20 µm around. Compared with most of commercial SPME fiber coatings, ANW SPME fiber coatings achieved the higher extraction capacity and special selectivity for volatile esters and alcohols. Finally, an efficient gas sampling technique based on ANW SPME fiber coating as the core was established and successfully applied for the ultra-selective determination of trace volatile esters and alcohols from complicated banana and fermented glutinous rice samples coupled with gas chromatography/mass spectrometry (GC/MS) detection. It was interesting that 25 esters and 2 alcohols among 30 banana volatile organic compounds (VOCs) identified and 4 esters and 7 alcohols among 13 identified VOCs of fermented glutinous rice were selectively sampled by ANW SPME fiber coatings. Furthermore, new analytical methods for the determination of some typical volatile esters and alcohols from banana and fermented glutinous rice samples at specific storage or brewing phases were developed and validated. Good recoveries for banana and fermented glutinous rice samples were achieved in range of 108-115% with relative standard deviations (RSDs) of 2.6-6.7% and 80.0-91.8% with RSDs of 0.3-1.3% (n=3), respectively. This work proposed a novel and efficient gas sampling technique of ANW SPME which was quite suitable for ultra-selectively sampling trace volatile esters and alcohols from complicated food samples.

Fabrication of novel nanoporous array anodic alumina solid-phase microextraction fiber coating and its potential application for headspace sampling of biological volatile organic compounds.

In the study, nanoporous array anodic alumina (NAAA) prepared by a simple, rapid and stable two-step anodic oxidization method was introduced as a novel solid-phase microextraction (SPME) fiber coating. The regular nanoporous array structure and chemical composition of NAAA SPME fiber coating was characterized and validated by scanning electron microscopy and energy dispersive spectroscopy, respectively. Compared with the commercial polydimethylsiloxane (PDMS) SPME fiber coating, NAAA SPME fiber coating achieved the higher enrichment capability (1.7-4.7 folds) for the mixed standards of volatile organic compounds (VOCs). The selectivity for volatile alcohols by NAAA SPME fiber coating demonstrated an increasing trend with the increasing polarity of alcohols caused by the gradually shortening carbon chains from 1-undecanol to 1-heptanol or the isomerization of carbon chains of some typical volatile alcohols including 2-ethyl hexanol, 1-octanol, 2-phenylethanol, 1-phenylethanol, 5-undecanol, 2-undecanol and 1-undecanol. Finally, NAAA SPME fiber coating was originally applied for the analysis of biological VOCs of Bailan flower, stinkbug and orange peel samples coupled with gas chromatography-mass spectrometry (GC-MS) detection. Thirty, twenty-seven and forty-four VOCs of Bailan flower, stinkbug and orange peel samples were sampled and identified, respectively. Moreover, the contents of trace 1-octanol and nonanal of real orange peel samples were quantified for the further method validation with satisfactory recoveries of 106.5 and 120.5%, respectively. This work proposed a sensitive, rapid, reliable and convenient analytical method for the potential study of trace and small molecular biological VOCs by the novel NAAA SPME fiber coating.

Preparation of styrene-co-4-vinylpyridine magnetic polymer beads by microwave irradiation for analysis of trace 24-epibrassinolide in plant samples using high performance liquid chromatography.

In the study, a kind of novel styrene-co-4-vinylpyridine (St-co-4-VP) porous magnetic polymer beads was prepared by microwave irradiation using suspension polymerization. Microwave heating preparation greatly reduced the polymerization time to 1h. Physical characteristic tests suggested that these beads were cross-linking and possessed spherical shape, good magnetic response and porous morphologies with a narrow diameter distribution of 70-180 µm. Therefore, these beads displayed the long-term stability after undergoing 100-time extractions. Then, an analytical method for the determination of trace 24-epiBR in plant samples was developed by magnetic polymer bead extraction coupled with high performance liquid chromatography-fluorescence detection. St-co-4-VP magnetic polymer beads demonstrated the higher extraction selectivity for 24-epiBR than other reference compounds. Linear range was 10.00-100.0 µg/L with a relative standard deviation (RSD) of 6.7%, and the detection limit was 6.5 µg/kg. This analytical method was successfully applied to analyze the trace 24-epiBR in cole and breaking-wall rape pollen samples with recoveries of 77.2-90.0% and 72.3-83.4%, respectively, and RSDs were less than 4.1%. The amount of 24-epiBR in real breaking-wall rape pollen samples was found to be 26.2 µg/kg finally. This work proposed a sensitive, rapid, reliable and convenient analytical method for the determination of trace brassinosteroids in complicated plant samples by the use of St-co-4-VP magnetic polymer bead extraction coupled with chromatographic method.

An improved facile method for extraction and determination of steroidal saponins in Tribulus terrestris by focused microwave-assisted extraction coupled with GC-MS.

An improved fast method for extraction of steroidal saponins in Tribulus terrestris based on the use of focus microwave-assisted extraction (FMAE) is proposed. Under optimized conditions, four steroidal saponins were extracted from Tribulus terrestris and identified by GC-MS, which are Tigogenin (TG), Gitogenin (GG), Hecogenin (HG) and Neohecogenin (NG). One of the most important steroidal saponins, namely TG was quantified finally. The recovery of TG was in the range of 86.7-91.9% with RSD<5.2%. The convention heating reflux extraction was also conducted in order to validate the reliability of this new FMAE method. The yield of total steroidal saponins was 90.3% in a one-step FMAE, while the yield of 65.0% was achieved during heating reflux extraction, and the extraction time was reduced from 3 h to 5 min by using less solvent. The method was successfully applied to analyze the steroidal saponins of Tribulus terrestris from different areas of occurrence. The difference in chromatographic characteristics of steroidal saponins was proved to be related to the different areas of occurrence. The results showed that FMAE-GC-MS is a simple, rapid, solvent-saving method for the extraction and determination of steroidal saponins in Tribulus terrestris.