Photoinduced Copper-Catalyzed Enantioconvergent Remote Alkynylation via 1,4-Heteroaryl Migration.

A photoinduced copper-catalyzed enantioconvergent remote alkynylation of N-hydroxyphthalimide esters with terminal alkynes via 1,4-heteroaryl migration has been developed. A broad scope of heteroaryl-tethered chiral alkynes has been synthesized with good regio- and enantioselectivities. The chiral-ligand-coordinated copper species plays a dual role as both the photoredox and cross-coupling catalyst. This methodology provides a new platform for enantioconvergent remote alkynylations.

Insights into the Mechanism of Bipolar Electrodeposition of Au Films and Its Application in Visual Detection of Prostate Specific Antigens.

Au particles are commonly used for deposition on the surface of a bipolar electrode (BPE) in order to amplify electrochemical and electrochemiluminescence (ECL) signal because of their excellent conductivity, biocompatibility, and large surface area. In this work, a closed BPE device was fabricated and Au particles were deposited on the two poles of a BPE via bipolar deposition. Results indicated that the electrochemical stability of Au film on the anode part of the BPE and the reduction of AuCl4- to Au on the cathode part of the BPE depended on the conductivity of the solution. The prepared Au-Au BPE exhibited a remarkable amplification effect on the ECL signal. Then, a specific sensing interface was constructed on one pole of the BPE for the visual detection of prostate-specific antigens (PSA) based on sandwich-type immunoreactions between primary PSA antibodies (Ab1) on the electrode surface, PSA, and SiO2 nanoparticles labeled secondary PSA antibodies (SiO2-Ab2). The designed biosensor exhibited a good linear relationship for the ECL detection of PSA in the range of 1 × 10-6 to 1 × 10-10 g/mL with a correlation coefficient of 0.9866; the limit of detection (LOD) was 1.5 × 10-11 g/mL. Additionally, the biosensor can realize the electrochemical imaging of PSA by regulating the electrochemical oxidation of the Au anode with the immunoreactions on the cathode part of BPE. Therefore, the small, portable and highly sensitive biosensors have great potential for on-site detection.

Cobalt-bismuth bimetallic composite anchored on carbon derived from cigarette butts as peroxymonosulfate activator for rapid removal of chloramphenicol.

Chloramphenicol (CAP) is a typical kind of antibiotics, which has posed a severe threat to nature and human beings due to its wide application. In this study, cobalt-bismuth bimetallic composite anchored on carbon derived from cigarette butts (Co-Bi@CCB) was prepared to activate peroxymonosulfate (PMS) for the removal of CAP. Our results demonstrated Co-Bi@CCB not only possessed excellent catalytic performance, but also significantly limited metal ions dissolution. Over 98% of CAP (10 mg/L) was degraded in the presence of Co-Bi@CCB (0.05 g/L) and PMS (1 mM) within 20 min at pH = 7. Quenching tests and electron paramagnetic resonance (EPR) spectrometry confirmed that SO4•-, •OH, and 1O2 led to the rapid decomposition of CAP. Combined with X-ray photoelectron spectroscopy (XPS) of Co-Bi@CCB before and after reaction, the mechanism of PMS activation was deduced. Finally, the possible pathways of CAP degradation was further speculated according to the intermediates determination by high-performance liquid chromatography equipped with high resolution mass spectrometer (HPLC-HRMS). Thus, the present study provides a new strategy to utilize discarded cigarette butts (recycled materials) as a carrier to fabricate novel and efficient catalysts to activate PMS for the removal of organic contaminants.

Rapid degradation of organic pollutants by Fe3O4@PDA/Ag catalyst in advanced oxidation process.

Over the past decades, the development of novel catalysts on the degradation of organic pollutants has attracted increasing attention. In this work, we synthesized silver decorated magnetic nanoparticles (Fe3O4@PDA/Ag NPs) to activate H2O2 for organic pollutants removal via advanced oxidation processes (AOPs). The catalyst was prepared through in-situ reduction of AgNO3 by the polydopamine (PDA) layer on Fe3O4 NPs. Chemiluminescence results obtained from luminol/H2O2 system revealed that the catalyst exhibited excellent catalytic effect on the decomposition of H2O2 into reactive oxygen species (ROS) and superoxide radical (O2-) was mainly responsible for the oxidative degradation. Importantly, the fast evolution frequency of oxygen gas bubbles produced in the reaction of Ag NPs and H2O2 could generate vigorous fluid convection and autonomous motion of catalyst when H2O2 concentration reached 1%. Additionally, the catalyst can suspend in solution for several minutes. Therefore, by coupling the vigorous motion with slow sedimentation velocity, the catalyst can realize rapid degradation of organic pollutants without external mixing force. The Fe3O4@PDA/Ag NPs catalysts not only showed a high removal efficiency of malachite green, but also can be applied for the degradation of other dyes, making it to be a promise candidate for environmental remediation. With the merits of excellent catalytic effect, fast degradation speed, and simplicity of operation, the prepared catalysts exhibits great potential in the practical field.

The Effects of the Combination of Oral Lactoferrin and Iron Injection on Iron Homestasis, Antioxidative Abilities and Cytokines Activities of Suckling Piglets.

Iron deficiency is considered a common nutritional problem for suckling piglets. The aim of this study was to evaluate the effects of the combination of oral lactoferrin and iron injection on iron levels, antioxidant ability and cytokine activity in suckling piglets. A total of sixty suckling piglets taken from six sows (10 piglets per litter) with a similar parity were chosen. The lactoferrin (LF) group was orally administrated with lactoferrin solution (0.5 g/kg body weight per day) for a week, the CON group was orally administrated with the same dose of physiological saline. Each piglet (all groups) was given 100 mg of iron dextran (FeDex) by intramuscular injection at the third day of age. Six piglets (n = 6) from each group were euthanized on days 8 and 21. The oral lactoferrin improved the iron level of suckling piglets by increasing the concentrations of serum hemoglobin and hepatic iron on day 8. Gene expression of lactoferrin receptor (LFR) was significantly increased in the LF group piglets on day 8, while duodenal protein expression of the divalent metal transporter 1 (DMT1) was significantly reduced in the LF group on day 8. In addition, oral lactoferrin enhanced serum T-AOC activities and duodenal SOD activities on day 21. The LF piglets had a significantly increased serum concentration of IL-10 on day 8. These results indicated that a combination of oral lactoferrin and iron injection is a more effective method of improving the iron level by up-regulating the expression of the LFR gene, enhancing the antioxidant ability and modulating the cytokine activity in the suckling piglets.

Dynamic changes of fatty acids and minerals in sow milk during lactation.

The objective of the present study was to explore the changes in fatty acids (FAs) and minerals composition in sow milk in order to improve the knowledge about FAs and mineral requirements for piglets. The FAs and minerals composition in the sow milk samples which were collected from ten sows during a period of 16 days of lactation was analysed. The proportion of FAs in sow milk has a significant increase in C8:0, C10:0, C12:0, C14:0, C16:0, C14:1 and C16:1 FAs and the sum of saturated fatty acids (SFAs) according to the lactation period (p < 0.05). The proportion of C18:2 cis-9,12 FA and the sum of polyunsaturated fatty acids (PUFAs) significantly decreased with the advancing of lactation (p < 0.05). The concentrations of minerals, including potassium, copper, manganese and zinc, were higher on day 1 and day 2 than those on day 13 and day 16 (p < 0.05). On the contrary, the lowest concentrations of calcium, sodium, magnesium and iron and the lowest molar calcium: phosphorus ratio emerged in colostrum (p < 0.05). In summary, our results demonstrated FAs profile and minerals concentrations were changed with lactation period. Better understanding of the changes of FAs and minerals may be valuable to swine nutritionists in the commercial industry. In addition, those results provided some meaningful information for sow's diet formulation during lactation.

[Aluminum dissolution and changes of pH in soil solution during sorption of copper by aggregates of paddy soil].

Size fractions of soil aggregates in Lake Tai region were collected by the low-energy ultrasonic dispersion and the freeze-desiccation methods. The dissolution of aluminum and changes of pH in soil solution during sorption of Cu2+ and changes of the dissolution of aluminum at different pH in the solution of Cu2+ by aggregates were studied by the equilibrium sorption method. The results showed that in the process of Cu2+ sorption by aggregates, the aluminum was dissoluted and the pH decreased. The elution amount of aluminum and the decrease of pH changed with the sorption of Cu2+, both increasing with the increase of Cu2+ sorption. Under the same conditions, the dissolution of aluminum and the decrease of pH were in the order of coarse silt fraction > silt fraction > sand fraction > clay fraction, which was negatively correlated with the amount of iron oxide, aluminum and organic matter. It suggested that iron oxide, aluminum and organic matters had inhibitory and buffering effect on the aluminum dissolution and the decrease of pH during the sorption of Cu2+.

Enhanced degradation of ortho-nitrochlorobenzene by the combined system of zero-valent iron reduction and persulfate oxidation in soils.

ortho-Nitrochlorobenzene (o-NCB) in soil poses significant health risks to human because of its persistence and high toxicity. The removal of o-NCB by both zero-valent iron (ZVI) and chemical oxidation (persulfate) was investigated by batch experiments. The o-NCB removal rate increases significantly from 15.1 to 97.3 % with an increase of iron dosage from 0.1 to 1.0 mmol g(-1). The o-NCB removal rate increases with the decrease of the initial solution pH, and a removal efficiency of 90.3 % is obtained at an initial pH value of 6.8 in this combined system. It is found that temperature and soil moisture could also increase the o-NCB removal rate. The o-NCB degradation rate increases from 83.9 to 96.2 % and from 41.5 to 82.4 % with an increase of temperature (15 to 35 °C) and soil moisture (0.25 to 1.50 mL g(-1)), respectively. Compared to the persulfate oxidation system and ZVI system, the persulfate-iron system shows high o-NCB removal capacity. o-NCB removal rates of 41.5 and 62.4 % are obtained in both the persulfate oxidation system and the ZVI system, while the removal rate of o-NCB is 90.3 % in the persulfate-iron system.

Determination of light-medium-heavy polycyclic aromatic hydrocarbons in vegetable oils by solid-phase extraction and high-performance liquid chromatography with diode array and fluorescence detection.

A new method for determination of 16 polycyclic aromatic hydrocarbons (PAHs)-naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene-in vegetable oils was developed. Solid-phase extraction (SPE) prior to high-performance liquid chromatography with fluorescence detection could be used for all those PAHs except acenaphthylene. Acenaphthylene could be detected using a diode array detector at 228 nm. The parameters and variables that affect the extraction were investigated. Under optimum conditions: the extract reagent was centrifuged at 4 °C and evaporated. After that a SPE procedure was used for further cleanup. The limits of detection and limits of quantification were in the range of 0.01-2.35 and 0.04-7.00 µg kg(-1) in vegetable oil, respectively. The relative standard deviations were under 5%.

Determination of four carbamate pesticides in corn by cloud point extraction and high-performance liquid chromatography in the visible region based on their derivatization reaction.

A highly sensitive method for the determination of arprocarb (AC), carbofuran (CF), isoprocarb (IC), and fenobucarb (FC) is proposed. The method is based on alkaline hydrolysis of the four carbamate pesticides, and the resultant hydrolysis products are reacted with 4-aminoantipyrene (AP) to give four red color products. The colored compounds are enriched and separated by cloud point extraction (CPE) method, and the coacervate phase containing the compounds is determined with a high-performance liquid chromatography (HPLC) system in the visible region. AC, CF, IC, and FC were determined on the basis of a linear correlation between the signals of the colored compounds and the concentrations of the pesticides. The method is applied to determine the four pesticides in corn samples; the limits of detection are 2.0 x 10(-4) mg L(-1) for AC, CF, and IC and 5.0 x 10(-4) mg L(-1) for FC, with recoveries ranging between 84.8 and 93.0%, at spiking levels of 5 x 10(-3), 2 x 10(-2), and 0.2 mg kg(-1), respectively.

Study of cloud point extraction and high-performance liquid chromatographic determination of isoniazid based on the formation of isonicotinylhydrazone.

Isoniazid (INH) reacted with p-dimethylaminobenzaldehyde (DABD) in the presence of trichloroacetic acid to give isonicotinylhydrazone (INZ) having lambda(max) 365nm. Cloud point extraction (CPE) is carried out to extract INH and IHZ in aqueous solutions using surfactant poly(ethylene glycol) 4000 (PEG4000), respectively. Langmuir model is used to study the adsorption behaviors of the two solutes on micelles of PEG4000. A linear correlation is found between variation of PEG4000 concentration required for feed concentration of the two solutes and used to predict PEG4000 concentration required for extracting INH and IHZ in CPE procedure. The results calculated show that, for a desired recovery level of 90%, only can IHZ be sufficiently extracted by PEG4000. In this experiment, the feed concentration of PEG4000 is defined by above-mentioned correlation, and the effects of other operating parameters, e.g., concentration of salt, pH and centrifugation time on extraction of PEG4000-IHZ system have also been studied in detail. The proposed CPE method coupled with HPLC-UV system is successfully used for the determination of INH in urine sample.