A STUDY ON THE SELECTIVE REDUCTION OF AROMATIC AMIDE WITH LiAlH_4

In the synthesis of l-phenyl-5-substituted amino-4-pyrazole N-alkyl amide, it was found for the first time that one of the two aromatic amido groups in the molecule of 1-phenyl-5-benzoyl amino-4-pyrazole N-alkyl amide was reduced selectively by LiAlH_4. new conclusion was drawn after several experiments have been done that ortho-amino(or substituted amino)aryl amide or the aryl amide with its ortho substituent which can be reduced into an amino group(or substituted amino group)can not be reduced by LiAlH_4. It was further rationalized by quantum chemical calculation.

Nodulin 26-like intrinsic protein Cs NIP2;2 is a silicon influx transporter in Cucumis sativus L.

Nodulin 26-like intrinsic proteins(NIPs) are a family of channel-forming transmembrane proteins that function in the transport of water and other small molecules.Some NIPs can mediate silicon transport across plasma membranes and lead to silicon accumulation in plants,which is beneficial for the growth and development of plants.Cucumber is one of the most widely consumed vegetables;however,the functions of NIPs in this crop are still largely unknown.Here,we report the functional characteristics of Cs NIP2;2.It was found that Cs NIP2;2 is a tandem repeat of Cs NIP2;1,which had been demonstrated to be a silicon influx transporter gene.Cs NIP2;2 has a selectivity filter composed of cysteine,serine,glycine and arginine(CSGR),which is different from all previously characterized silicon influx transporters in higher plants at the second helix position.Xenopus laevis oocytes injected with Cs NIP2;2 c RNA demonstrated a higher uptake of silicon than the control,and the uptake remained unchanged under low temperature.Cs NIP2;2 was found to be expressed in the root,stem,lamina and petiole,and exogenous silicon treatment decreased its expression in the stem but not in other tissues.Transient expression of Cs NIP2;2-e GFP fusion sequence in onion epidermal cells showed that Cs NIP2;2 was localized to the cell nucleus,plasma membrane and an unknown structure inside the cell.The results suggest that Cs NIP2;2 is a silicon influx transporter in cucumber,and its subcellular localization and the selectivity filter are different from those of the previously characterized silicon influx transporters in other plants.These findings may be helpful for understanding the functions of NIPs in cucumber plants.

Facile Preparation of Fluoroalkyl End-Capped Vinyltrimethoxysilane Oligomer/Sand Composites Possessing Superoleophilic/Superhydrophobic Characteristic: Application to Oil/Water Separation and Selective Removal of Fluorinated Aromatic Compounds from Aqueous Methanol Solution

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2-CHSi(OMe)3)n-RF: n = 2, 3, RF = CF(CF3)OC3F7: RF-(VM)n-RF], was applied to the facile preparation of the corresponding oligomer/sand (Ottawa sand: OS) composites [RF-(VM-SiO3/2)n-RF/OS] through the sol-gel reaction of the oligomer in the presence of micro-sized OS particles (590 - 840 μm) under alkaline conditions at room temperature. FE-SEM (Field Emission Scanning Electron Micrograph) images showed that the obtained composites consist of the RF-(VM-SiO3/2)n-RF oligomeric nanoparticles and the micro-sized OS particles. Interestingly, the RF-(VM-SiO3/2)n-RF/OS composites thus obtained can provide the superoleophilic/superhydrophobic characteristic on the composite surface, applying to the separation of not only the mixture of oil/water but also the W/O emulsion to isolate the transparent colorless oil. The fluorinated oligomeric OS composites were also found to be applicable to the selective removal of fluorinated aromatic compounds from an aqueous methanol solution. Especially, it was demonstrated that the fluorinated OS composites can supply a higher efficient and smooth separation ability for the separation of the mixture of oil and water than that of the corresponding fluorinated micro-sized controlled silica gel (μ-SiO2) composites (average particle size: 9.5 μm), which were prepared under similar conditions. In addition to the separation of oil/water, the fluorinated OS composites provided higher and more selective removal ability for the fluorinated aromatic compounds from aqueous solutions than that of the μ-SiO2 composites.

Targeted synthesis of novel porous aromatic frameworks with selective separation of CO_2/CH_4and CO_2/N_2

Novel porous aromatic frameworks（PAF-53 and PAF-54） have been obtained by the polymerization of amino compound（p-phenylenediamine and melamine） and cyanuric chloride. They display a certain amount of CO2 adsorption capacity and highly selective separation of CO2/CH4 and CO2/N2 as 18.1 and83 by Henry Law respectively. They may be applied as ideal adsorbents to separate and capture CO2.

Porous boronate affinity monolith for on-line extraction coupled to high-performance liquid chromatography for sensitive analysis of heterocyclic aromatic amines in food samples

A novel on-line solid-phase microextraction–high-performance liquid chromatography（SPME–HPLC）system was developed for the determination of heterocyclic aromatic amines（HAAs） in food samples. A poly（vinylphenylboronic acid-co-ethylene glycol dimethacrylate） polymer monolith was prepared for on-line efficient extraction and large-volume injection was used to increase the sensitivity of detection.The polymermonolith, based on a ternary porogen, was prepared by in situ polymerization of vinylphenylboronic acid（VPBA） and ethylene glycol dimethacrylate（EGDMA） in a fused-silica capillary column. It showed good permeability, high extraction capacity, and high selectivity. The column-tocolumn reproducibility was satisfactory, and the enrichment factors for HAAs were 3746–7414.Conditions influencing the on-line extraction efficiency, including p H of sample solutions, flow rate of extraction and desorption, and desorption volume, were investigated. The proposed method had low limit of detection（0.10–0.15 ng/L） and good linearity. Trace HAAs in roast beef and lamb samples were determined, and the amounts of 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline, and 2-amino-3,4,7,8-tetramethyl-3H-imidazo[4,5-f]quinoxaline in these samples were 0.235–2.08 ng/g. The recoveries for the five HAAs ranged from74.3% to 119%, and the relative standard deviation（RSDs） were less than 8.2%. The results showed that the proposed on-line method was highly sensitive for monitoring HAAs in different food samples.

Aromatic alcohols oxidation and hydrogen evolution over π-electron conjugated porous carbon nitride rods

Photocatalysis using polymeric carbon nitride(CN)materials is a constantly evolving field,where the variation of synthetic procedures allows the constant improvement of activity by tackling the intrinsic limitations of these materials(optical absorbance,specific surface area,charge migration,etc.).Amongst the possible photocatalytic reactions,the most popular application of CNs is the hydrogen evolution reaction(HER)from water.In this work,we design precisely-controlled carbon-doped porous CN rods with extended π-electron conjugation from supramolecular assemblies of melem and co-monomers,which partially substitute nitrogen for carbon atoms at the pyrimidine ring of the melem.Dense hydrogen bonds and good thermal stability of the melem-based supramolecular framework allow synthesizing a more ordered structure for improved charge migration;the control from the molecular level over the position of carbon-substituted nitrogen positions tailors the band alignment and photogenerated charge separation.The optimal photocatalyst shows an excellent HER rate(up to 10.16 mmol·h-1·g-1 under 100 W white light-emitting diode(LED)irradiation,with an apparent quantum efficiency of 20.0%at 405 nm,which is 23.2 times higher compared to a reference bulk CN).To fully harness the benefits of the developed metal-free CNs,selective oxidation reaction of aromatic alcohols is demonstrated with high conversion and selectivity.

Copper-catalyzed 1,3-dipolar cycloaddition of methyleneindolinones and N,N'-cyclic azomethine imines

A copper-catalyzed stereoselective 1,3-dipolar cycloaddition of methyleneindolinones and N,N0-cyclic azomethine imines has been developed under mild reaction conditions.The spiro[pyrazolidin-3,30-oxindoles] were obtained in moderate to high isolated yields（up to 82%） with good stereoselevtivities（up to 15：1） in the presence of 5 mol% of Cu（OAc）2at room temperature.