Pesticide‐conjugated polyacrylate nanoparticles: novel opportunities for improving the photostability of emamectin benzoate

Emamectin benzoate, a macrocyclic lactone, can be used in low quantities to control arthropod pests, effectively. However, its poor photostability prevents its further use. To delay its photodegradation, novel acrylate‐type polymeric nanoparticles were synthesized and tested as materials for improving pesticide photostability. N‐acylated emamectin benzoate was synthesized via bonding emamectin benzoate to acrylamide. The resulting pesticide, containing the double bond linkage –C=C–N–, was copolymerized with butyl acrylate and methyl methacrylate by the emulsion polymerization method. The refined polymers were characterized by Fourier transform infrared spectroscopy spectroscopy, and result illustrated the pesticide was conjugated to the polymers. Atomic force microscope and dynamic light scattering analyses were also used for determining the average particle diameters of pesticide–polymer conjugates. Photostability tests showed that the nanoparticles obtained exhibited greatly improved photostability. Additionally, the laboratory toxicity tests demonstrated that the insecticidal effects of the novel emamectin benzoate formulation were better than those of the control pesticide formulation (emamectin benzoate EC). Copyright © 2012 John Wiley & Sons, Ltd.     

Design of Sensitive Biocompatible Quantum‐Dots Embedded in Mesoporous Silica Microspheres for the Quantitative Immunoassay of Human Immunodeficiency Virus‐1 Antibodies

A novel sandwich‐type electrochemiluminescence (ECL) immunosensor was developed to enable the sensitive detection of HIV‐1 antibodies. This system incorporated mesoporous silica (mSiO₂) complexed with quantum dots (QDs) and nano‐gold particles, which were assembled to enhance signal detection. Magnetic beads were used by immobilizing the secondary anti‐IgG antibody. This was first employed to capture HIV‐1 antibody (Ab) to form a Fe₃O₄/anti‐IgG/Ab complex. A high loading and signal‐enhanced nanocomposite (hereafter referred to as Au‐mSiO₂‐CdTe) was used as a HIV‐1 antigen label. The Au‐mSiO₂‐CdTe nanocomposite was conjugated with the Fe₃O₄/anti‐IgG/Ab complex to form an immunocomplex (hereafter referred to as Fe₃O₄/anti‐IgG/Ab/HIV‐1/CdTe‐mSiO₂‐Au). This complex could be further separated by an external magnetic field to produce ECL signals. Due to the large specific surface area and pore volume of mSiO₂, the loading of the CdTe QDs was markedly increased. Thus, the loaded QDs released a powerful chemiluminescent signal with a concordantly increased sensitivity of the immunosensor. The immunosensor was highly sensitive, and displayed a linear range of responses for HIV‐1 antibody across a dilution range of 1 : 1500 through 1 : 50 with the detection limit of 1 : 4500. The immunoassay can be a promising candidate in early diagnosis of HIV infection.     

Identification of urinary metabolites of imperatorin with a single run on an LC/Triple TOF system based on multiple mass defect filter data acquisition and multiple data mining techniques

The detection of drug metabolites, especially for minor metabolites, continues to be a challenge because of the complexity of biological samples. Imperatorin (IMP) is an active natural furocoumarin component originating from many traditional Chinese herbal medicines and is expected to be pursued as a new vasorelaxant agent. In the present study, a generic and efficient approach was developed for the in vivo screening and identification of IMP metabolites using liquid chromatography-Triple TOF mass spectrometry. In this approach, a novel on-line data acquisition method mutiple mass defect filter (MMDF) combined with dynamic background subtraction was developed to trace all probable urinary metabolites of IMP. Comparing with the traditionally intensity-dependent data acquisition method, MMDF method could give the information of low-level metabolites masked by background noise and endogenous components. Thus, the minor metabolites in complex biological matrices could be detected. Then, the sensitive and specific multiple data-mining techniques extracted ion chromatography, mass defect filter, product ion filter, and neutral loss filter were used for the discovery of IMP metabolites. Based on the proposed strategy, 44 phase I and 7 phase II metabolites were identified in rat urine after oral administration of IMP. The results indicated that oxidization was the main metabolic pathway and that different oxidized substituent positions had a significant influence on the fragmentation of the metabolites. Two types of characteristic ions at m/z 203 and 219 can be observed in the MS/MS spectra. This is the first study of IMP metabolism in vivo. The interpretation of the MS/MS spectra of these metabolites and the proposed metabolite pathway provide essential data for further pharmacological studies of other linear-type furocoumarins.     

New Cytotoxic Triterpenoids from the Aerial Parts of Euphorbia sieboldiana

Phytochemical investigation of the EtOH extract of Euphorbia sieboldiana led to the isolation of four new oleanane‐type triterpenoids, (1β,2α,3β,19β)‐1,2,3,19‐tetrahydroxyolean‐12‐en‐28‐oic acid, (1β,3β,19β)‐1,3,19‐trihydroxyolean‐12‐en‐28‐oic acid, (1β,2α,3β,16β,19β)‐1,2,3,16,19‐pentahydroxyolean‐12‐en‐28‐oic acid, and (1β,2α,3β,19β,23)‐1,2,3,19,23‐pentahydroxyolean‐12‐en‐28‐oic acid, along with 16 known compounds. Their structures were established by extensive 1D‐ and 2D‐NMR, as well as other spectral analyses. Biological evaluation of the four new triterpenoids revealed potent cytotoxic activities against HeLa and Hep‐G2 cells.     

An Efficient Synthesis of New Dispiropyrrolidine Derivatives via Three‐Component 1,3‐Dipolar Cycloaddition Reaction

A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, ¹H‐NMR, and HRMS spectra.     

Efficient Green Procedure for the Synthesis of Coumarin Derivatives by a One‐Pot,Three‐Component Reaction under Solvent‐Free Conditions

A simple, efficient, and general method has been developed for the synthesis of coumarin derivatives through a one‐pot reaction of aromatic aldehydes, 2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione and 5,5‐dimethyl‐1,3‐cyclohexanedione, in the presence of TEBA under solvent‐free conditions using grinding methods. The mild reaction conditions, simple protocol, high yields, and cleaner reaction make this protocol practical and economically attractive.     

Ammonium Chlorochromate Adsorbed on Silica Gel: A New Reagent for the Oxidation of Alcohols and Benzoins to Corresponding Carbonyl Compounds

A new reagent, Ammonium chlorochromate adsorbed on silica gel, suitable for the oxidation of alcohols and benzoins to the corresponding carbonyl compounds is described.     

Phosphate Removal from Aqueous Solution by an Effective Clay Composite Material

Adsorption is an effective treatment process for removing phosphorus and thus controlling eutrophication. In this study, a clay composite material called Al–dolomite–montmorillonite (Al–DM) was prepared and characterized. Al–DM performed well with respect to phosphate removal, with its performance depending on the Al–DM loading, contact time, initial phosphorus concentration and initial solution pH. Adsorption mechanisms were investigated by conducting batch tests on phosphate adsorption using the Al–DM. The adsorption process fitted both the pseudo-second-order kinetics model and the intra-particle diffusion model. The Langmuir, Freundlich and BET models all adequately described the adsorption isotherm data. Thermodynamic studies showed that the adsorption process was endothermic and spontaneous in nature. Al–DM is an effective adsorbent for phosphate removal mainly due to its hierarchical porous structures as shown by characterization with SEM and EDS. Chemical changes occurring before and after adsorption in a water environment indicated that Al–DM had little negative effect on water quality.