Rapid Detection of Five Estrogens Added Illegally to Dietary Supplements by Combining TLC with Raman Imaging Microscope

Estrogens added illegally to dietary supplements are hazardous to human health. Traditional detection and analysis methods have many limitations, and we have developed an assay that combines thin-layer chromatography with Raman imaging microscopy (TLC-RIM). The five estrogens (estrone, estradiol, estriol, ethinyl estradiol, and diethylstilbestrol) were initially separated by TLC, then detected by area scanning Raman imaging with a 532 nm laser under a microscope. Raman spectra were obtained for each estrogen, which were used for detecting estrogen illegally added to botanical dietary supplements. The LOD of each estrogen was 0.4, 1.0, 0.8, 0.2, and 0.2 mg/mL, respectively. The matrix in the real sample did not interfere with the detection of estrogens. The method was fast, sensitive, stable, specific, and reliable.     

Impact of the Acetaldehyde-Mediated Condensation on the Phenolic Composition and Antioxidant Activity of Vitis vinifera L. Cv. Merlot Wine

Acetaldehyde is a critical reactant on modifying the phenolic profile during red wine aging, suggesting that the acetaldehyde-mediated condensation can be responsible for the variation of antioxidant activity during the aging of this beverage. The present study employs exogenous acetaldehyde at six levels of treatment (7.86 ± 0.10–259.02 ± 4.95 mg/L) before the bottle aging of Merlot wines to encourage phenolic modification. Acetaldehyde and antioxidant activity of wine were evaluated at 0, 15, 30, 45, 60 and 75 days of storage, while monomeric and polymeric phenolics were analyzed at 0, 30 and 75 days of storage. The loss of acetaldehyde was fitted to a first-order reaction model, the rate constant (k) demonstrated that different chemical reaction happened in wines containing a different initial acetaldehyde. The disappearance of monomeric phenolics and the formation of polymeric phenolics induced by acetaldehyde could be divided into two phases, the antioxidant activity of wine did not alter significantly in the first phase, although most monomeric phenolics vanished, but the second phase would dramatically reduce the antioxidant activity of wine. Furthermore, a higher level of acetaldehyde could shorten the reaction time of the first phase. These results indicate that careful vinification handling aiming at controlling the acetaldehyde allows one to maintain prolonged biological activity during wine aging.     

Ag/CNT‐catalyzed hydroamination of activated alkynes with aromatic amines

As a nanoparticle support material, carbon nanotubes (CNTs) provide a certain potential activation of catalysis in heterogeneous catalytic organic reactions. Herein, an efficient Ag/CNT‐catalyzed synthesis of enamines via hydroamination of activated alkynes with aromatic amines has been described. This catalyst still retains catalytic activity after being recycled and reused three times. In addition, it represents a green and environmentally friendly process for preparation of enamines. Copyright © 2013 John Wiley & Sons, Ltd.     

Approach for the Direct Synthesis of β-Dichlorosubstituted Acetanilides Using Iodine Trichloride (ICl3) as the Oxidant and Catalyst

A reliable method for direct synthesis of β‐dichlorosubstituted acetanilides is reported. The key transformation involves the oxidative and catalytic cleavage of a carbon‐carbon bond in the presence of iodine trichloride (ICl₃). In this protocol ICl₃ is used not only as the catalyst but also as the oxidant which widely broadens the scope of its application in organic synthetic chemistry.     

Synthesis, structure, and activity evaluation of two silver(I) complexes as Helicobacter pylori urease inhibitors

Two silver(I) compounds, [Ag(R,R-hxn)](C₇H₄BrO₂) · 2H₂O (I) (Chxn = 1,2-diaminocyclohexane) and [Ag(C₅H₆N₂)₂]₂(C₈H₄O₄) · 10H₂O (II), were synthesized and complex I was structurally characterized by X-ray crystallography. Compound I contains a catena-(trans-1,2-diaminocyclohexane) silver polycation ([Ag(Chxn)]_∞) in a roughly linear fashion, while II possesses a linear-type silver monocation. Compounds I and II were evaluated for their inhibitory activities against Helicobacter pylori urease in vitro. Both were found to have strong inhibitory activities against H. pylori urease comparable to that of acetohydroxamic acid.     

A new application of multiwavelets: Discrimination of marine algae taxonomic groups with emission-excitation matrix fluorescence

The 3D fluorescence discrimination of phytoplankton classes was investigated by SA4 multiwavelet,GHM multiwavelet,and coifman-2(coif2) wavelet analysis.Belonging to 35 genera of 7 major phytoplankton divisions in the inshore area of China Sea,Single species cultures of 51 phytoplankton species were employed.The second scale vector (Ca2) of SA4,Ca2 of GHM and the third scale vector (Ca3) of coif2 were selected as feature spectra by Bayesian discriminate analysis (BDA).The reference spectra were obtained via hierarchical cluster analysis (HCA).With average high correct discrimination ratios (CDRs),reference spectra were representative to phytoplankton species.For one-algae samples,the average CDRs were 95.6% at genus level and 86.7% at division level.For the laboratory mixed samples,the average CDRs (one division accounted for 25%,75% or 100% of the total biomass) were 86.6%,91.4% and 100% at division level.Moreover,the average CDRs of the dominant species (accounted for 75%) was 79.8% at genus level.Results for the in situ samples were coincided with the microscopic ones at division level with the relative contents of 54.3%-96.5%.The fluorometric discriminating technique was further tested during the cruise in Bohai Sea recently.     

Alginate‐Based Microcapsules with a Molecule Recognition Linker and Photosensitizer for the Combined Cancer Treatment

A reactive template method was used to fabricate alginate‐based hydrogel microcapsules. The uniform and well‐dispersed hydrogel capsules have a high drug loading capacity. After they are coated by a folate‐linked lipid mixture on the surface, the capsules possess higher cell uptake efficiency by the molecule recognition between folate and the folate‐receptor overexpressed by the cancer cells. Moreover, in this bioconjugate, the lipid could remarkably reduce the release rate of hydrophilic doxorubicin from the hydrogel microcapsules and encapsulate the hydrophobic photosensitizer hypocrellin B. The biointerfaced capsules could be used as drug carriers for combined treatment against cancer cell proliferation in vitro; this was much more effective than chemotherapy or photodynamic therapy alone.     

Highly selective synthesis of single-walled carbon nanotubes from methane in a coupled Downer-turbulent fluidized-bed reactor

For the synthesis of single-walled carbon nanotubes (SWCNTs) from CH₄ over a Fe/MgO catalyst, we proposed a coupled Downer-turbulent fluidized-bed (TFB) reactor to enhance the selectivity and yield (or production rate) of SWCNTs. By controlling a very short catalyst residence time (1–3 s) in the Downer, only part of Fe oxides can be reduced to form Fe nano particles (NPs) available for the growth of SWCNTs. The percentage of unreduced Fe oxides increased and the yield of SWCNTs decreased accordingly with the increase of catalyst feeding rate in Downer. SWCNTs were preferentially grown on the catalyst surface and inhibited the sintering of the Fe crystallites which would be formed thereafter in the downstream TFB, evidenced by TEM, Raman and TGA. The coupled Downer-turbulent fluidized-bed reactor technology allowed higher selectivity and higher production rate of SWCNTs as compared to TFB alone.     

Preparation of Hyaluronic Acid Micro-Hydrogel by Biotin–Avidin-Specific Bonding for Doxorubicin-Targeted Delivery

Hyaluronic acid is a naturally ionic polysaccharide with cancer cell selectivity. It is an ideal candidate material for delivery of anticancer agents. In this study, hyaluronic acid (HA) micro-hydrogel loaded with anticancer drugs was prepared by the biotin–avidin system approach. Firstly, carboxyl groups on HA were changed into amino groups with adipic acid dihydrazide (ADH) to graft with biotin by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride named as HA–biotin. When HA–biotin solution mixed with doxorubicin hydrochloride (DOX·HCl) was blended with neutravidin, the micro-hydrogels would be formed with DOX loading. If excess biotin was added into the microgel, it would be disjointed, and DOX will be released quickly. The results of the synthesis procedure were characterized by ¹H-NMR and FTIR; ADH and biotin have been demonstrated to graft on the HA molecule. A field emission scanning electron microscope was used to observe morphologies of HA micro-hydrogels. Furthermore, the in vitro DOX release results revealed that the release behaviors can be adjusted by adding biotin. Therefore, the HA micro-hydrogel can deliver anticancer drugs efficiently, and the rate of release can be controlled by biotin-specific bonding with the neutravidin. Consequently, the micro-hydrogel will perform the promising property of switching in the specific site in cancer therapy.