P-P Condensation and P-N/P-P Bond Metathesis: Facile Synthesis of Cationic Tri- and Tetraphosphanes.

[LC R P((PhP)2 C2 H4 )][OTf] (4 a,b[OTf]) and [LC iPr P(PPh2 )2 ][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [LC R P(pyr)2 ][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; LC R =1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C2 H4 P(H)Ph) and Ph2 PH. A stepwise double P-N/P-P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph2 P)2 (LC Me P)2 ][OTf]2 (7 a[OTf]2 ) is observed when reacting 3 a[OTf] with diphosphane P2 Ph4 . The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3 CN)4 ]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2 PPLC iPr )Au}4 ][OTf]4 (9[OTf]4 ) was unexpectedly formed as a result of a chloride-induced P-P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH3 CN)3 ][OTf]2 (M=Cu, Ag) (10[OTf]2 , 11[OTf]2 ).

Prevalence of polycystic ovary syndrome in Thai University adolescents.

Polycystic ovarian syndrome (PCOS) is a common and complex condition characterized by endocrine features and influenced by genetic and environmental factors. In Southeast Asia and Thailand, the prevalence of PCOS is unknown. The aim of this study was to estimate the prevalence of and determine factors associated with PCOS in Thai adolescents. We administered a validated questionnaire to 600 university female participants aged 17-19 years from Mahidol University in Bangkok. Of these, 548 (91.33%) responded and agreed to participate. Two-hundred and seventy-nine girls (50.91%) were identified as likely having PCOS and defined as 'probable cases'. Of those 279 participants, 248 (88.88%) were evaluated further for PCOS using the Rotterdam criteria. A complete history was taken, and a physical examination including trans-abdominal ultrasound was performed. Blood chemistry tests were performed to exclude similar conditions and to investigate potential co-morbidities. The prevalence of PCOS in Thai adolescents was found to be 5.29%. After multivariate analyses, moderate acne was the strongest risk factor for PCOS. The odd ratios (95% confidence interval) for the presence of mild acne, moderate acne, and oligo- or amenorrhea in participants with PCOS were 2.83 (1.01-7.90; p = .47), 31.69 (10.07-99.67; p < .001), and 5.89 (2.42-14.37; p < .001), respectively.

Effect of K+ and Ca2+ Cations on Structural Manganese(IV) Oxide for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

The promising influences of K+ and Ca2+ ions in the development of effective MnO2 for the selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA) were studied for the catalytic performance under a high-pressure reaction of aqueous O2 (0.5 MPa) in a basic system. Various oxidation states of manganese in MnO2 were able to accelerate the oxidation of 5-formyl-2-furancarboxylic acid to FDCA in the rate-determining step. The results were in good agreement that Ca2+ played a key role in the highest FDCA yield up to 85% due to the associated cations on the local coordination to enhance the high surface area and the electronic effect on the manganese ion. Both K-MnO2 and Ca-MnO2 catalysts showed excellent catalytic activities without a significant change in the efficiency in the reusability experiments.

One-pot synthesis of iron oxide - Gamma irradiated chitosan modified SBA-15 mesoporous silica for effective methylene blue dye removal.

The development of adsorption technology and the processing of radiation have both been influenced by chitosan adsorbent (γ-chitosan), a raw material with unique features. The goal of the current work was to improve the synthesis of Fe-SBA-15 utilizing chitosan that has undergone gamma radiation (Fe-γ-CS-SBA-15) in order to investigate the removal of methylene blue dye in a single hydrothermal procedure. High-resolution transmission electron microscopy (HRTEM), High angle annular dark field scanning transmission electron microscopy (HAADF-STEM), small- and wide-angle X-ray powder diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR) and Energydispersive X-ray spectroscopy (EDS) were used to characterize γ-CS-SBA-15 that had been exposed to Fe. By using N2-physisorption (BET, BJH), the structure of Fe-γ-CS-SBA-15 was investigated. The study parameters also included the effect of solution pH, adsorbent dose and contact time on the methylene blue adsorption. The elimination efficiency of the methylene blue dye was compiled using a UV-VIS spectrophotometer. The results of the characterization show that the Fe-γ-CS-SBA-15 has a substantial pore volume of 504 m2 g-1 and a surface area of 0.88 cm3 g-1. Furthermore, the maximum adsorption capacity (Qmax) of the methylene blue is 176.70 mg/g. The γ-CS can make SBA-15 operate better. It proves that the distribution of Fe and chitosan (the C and N components) in SBA-15 channels is uniform.

Low-temperature carbon-chlorine bond activation by bimetallic gold/palladium alloy nanoclusters: an application to Ullmann coupling.

This paper describes the unique catalytic activity of bimetallic Au/Pd alloy nanoclusters (NCs) for Ullmann coupling of chloroarenes in aqueous media at low temperature. The corresponding reaction cannot be achieved by monometallic Au and Pd NCs as well as their physical mixtures. On the basis of quantum chemical calculation, it was found that the crucial step to govern the unusual catalytic activity of Au/Pd is the dissociative chemisorption of ArCl, which is unlikely in the monometallic Au and Pd NCs.

Synthesis and reactivity of nitrogen nucleophiles-induced cage-rearrangement silsesquioxanes.

Novel phthalimide and o-sulfobenzimide-functionalized silsesquioxanes were successfully synthesized via nucleophilic substitution reactions from octakis(3-chloropropyl)octasilsesquioxane. Surprisingly, the formation of deca- and dodecasilsesquioxanes cages was discovered during substitution with phthalimide, but only octasilsesquioxane maintained a cage in the o-sulfobenzimide substitution reaction. Moreover, we report the electronic effect of nitrogen nucleophiles to promote cage-rearrangement of inorganic silsesquioxane core for the first time. Structures of products were confirmed by (1)H, (13)C, and (29)Si NMR spectroscopy, ESI-MS analysis, and single-crystal X-ray diffraction.

Electrocatalytic oxidation of ascorbic acid using a poly(aniline-co-m-ferrocenylaniline) modified glassy carbon electrode.

A poly(aniline-co-m-ferrocenylaniline) was successfully synthesized on a glassy carbon electrode (GCE) by electrochemical copolymerization using a scan potential range from -0.3 to +0.9 V (vs. Ag/AgCl) in 0.5 M H2SO4 containing 30% acetonitrile (ACN), 0.1 M aniline (Ani) and 0.005 M m-ferrocenyaniline (m-FcAni). The field emission scanning electron microscope (FESEM) and electrochemical methods were used to characterize the poly(Ani-co-m-FcAni) modified electrode. The poly(Ani-co-m-FcAni)/GCE exhibited excellent electrocatalytic oxidation of ascorbic acid (AA) in citrate buffer solution (CBS, pH 5.0). The anodic peak potential of AA was shifted from +0.55 V at the bare GCE to +0.25 V at the poly(Ani-co-m-FcAni)/GCE with higher current responses than those seen on the bare GCE. The scan number at the 10th cycle was selected as the maximum scan cycle in electrochemical polymerization. The limit of detection (LOD) was estimated to be 2.0 µM based on the signal-to-noise ratio (S/N = 3). The amperometric responses demonstrated an excellent selectivity for AA determination over glucose (Glu) and dopamine (DA).

Hydrogel-Templated Solid Base Catalysts for Transesterification of Soybean Oil.

A new method for utilization of hydrogel is proposed here for the preparation of solid base catalysts for the transesterification of vegetable oil. When a solution of KF is mixed with a solution of Ca(NO3)2, CaF2 is obtained and inactive as a catalyst in the transesterification of vegetable oils. The catalysts were synthesized by the sequential incorporation of KF and/or Ca(NO3)2 solutions into the hydrogel upon microwave irradiation and then the as-obtained hydrogel was calcined at 800°C for 5 hours to eliminate the template and yield catalysts for the biodiesel productions. The prepared catalysts obtained by the different ways in the incorporation of ions into the hydrogel showed different physical properties and catalytic activities in the transesterification of soybean oil. All catalysts, except the low concentration of Ca(NO3)2, exhibiting the high activity yielding more than 90% FAME after 1 hour at 65°C, using oil to methanol molar ratio of 1:15 and 10 wt% of catalyst amounts.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE.

Esterification of fatty acid catalyzed by hydrothermally stable propylsulfonic acid-functionalized mesoporous silica SBA-15.

Propylsulfonic acid-functionalized mesoporous silica SBA-15 has been synthesized via one-step strategy at 130°C based on the co-condensation of TEOS and MPTMS in the presence of Pluronic 123 polymer and H2O2 in HCl aqueous solution. The synthesized solid exhibited hydrothermal stability in boiling water without significant change in textural properties. The catalytic performance of the synthesized solid was studied in the esterification of oleic acid with methanol. The experimental results revealed that the large mesopore structures of SBA-15-PrSO3H solid synthesized at 130°C could favor a facile access of oleic acid to the acid sites, making the comparable activity to that of phenyl ethyl sulfonic acid functionalized silica and higher than that of dry amberlyst-15.

Aryl iodides as strong inhibitors in gold and gold-based bimetallic quasi-homogeneous catalysis.

The strong inhibitor effect of aryl iodides on the quasi-homogenous gold-catalyzed oxidation reaction was described. Aryl iodides were adsorbed on the exposed surface of Au clusters, which affected the accessibility of the nanoclusters to the reacting species and acted as strong inhibitors in catalysis.