Transient and Recyclable Halogenation Coupling (TRHC) for Isoflavonoid Synthesis with Site-Selective Arylation

A transient and recyclable C−H iodination has been designed for the synthesis of isoflavonoids through the domino reactions of o-hydroxyphenyl enaminones and aryl boronic acids in the presence of catalytic KI and Pd catalyst. Instead of the conventional cross-coupling strategy employing pre-halogenated substrates, this method transforms raw C−H bond by means of a transient C−H halogenation to smoothly relay the subsequent C-arylation. Consequently, such a method avoids the pre-functionalization for C−halogen bond installation as well as the generation of stoichiometric halogen-containing waste following the cross-coupled product, disclosing an intriguing new coupling protocol to forge the C−C bond in the virgin area between classical C−X (X=halogen) bond cross coupling and the C−H activation.     

Preparation and Tribological Behaviors of Lubricants—Oil Based on Modified Microbial Oil with Nano-Schiff Base Copper Complex

A W/O microemulsion reactor was used to prepare four kinds of modified lubricants: (i) modified lubricant 1, modified epoxidized microbial oil + rape oil in volume ratio of 1:1; (ii) modified lubricant 2, modified esterified microbial oil + rape oil in volume ratio of 1:3; (iii) modified lubricant 3, modified epoxidized rape oil; and (iv) modified lubricant 4, modified PAO. The individual modified lubricants were further modified with 0%, 0.5%, 1%, and 2% content of nano-Schiff base copper complex (nano-SBCC). A microtribometer was used to evaluate the friction coefficient between ball/flat point contacts immersed in the modified lubricants and operated in reciprocating and linear sliding mode. A comparison of the values of the friction coefficient with the lubricants further modified with nano-SBCC with those of their individual 0% nano-SBCC counterparts indicated significant decrease: (i) almost 19.18% was obtainable for the modified lubricant 1 with 2% of nano-Schiff base copper complex, (ii) almost 16.5% was obtainable for the modified lubricant 2 with 0.5% of nano-Schiff base copper complex; (iii) almost 7.42% was obtainable for the modified lubricant 3 with 1% of nano-SBCC; and (iv) almost 7.01% was obtainable for the modified lubricant 4 with 0.5% of nano-SBCC. These suggested that the addition of nano-Schiff base copper complex can efficiently decrease the friction coefficient of epoxidized or esterified microbial oil. Analyses of two-dimensional images, average profiles (across the mid-section y = 0 of the reciprocating sliding path), and three-dimensional topographies by confocal white light microscope for the worn surfaces of flats immersed in modified lubricant 1 and modified lubricant 2 suggested better wear-resistance of the modified lubricant 2 than that of the modified lubricant 1. The ability of wear resistance for the modified lubricant became better with the increasing content of nano-Schiff base copper complex from 0% to 2%. The study revealed the modification of epoxidized microbial oil + rape oil (1:1 volume ratio) and esterified microbial oil + rape oil (1:3 volume ratio) with Cu(II) chelate of bis(salicylaldehyde)ethylenediamine, reducing the magnitude of friction and wear because of their respective wear self-repairing ability. Such self-repairing ability furnishes the suitability of epoxidized microbial oil or esterified microbial oil to be effectively modified by nano-Schiff base copper complex and to substitute ordinary base oil as a mixture with rape oil.     

Toward the natural didemnaketal A: total synthesis of the isomer of didemnaketal A

The total synthesis of isomer of didemnaketal A was achieved in 26 steps. The position of esters is switched at C7 and C8 with respect to their proposed position in natural didemnaketal A, which shows potent anti-HIV activity but so far has not been synthesized in the laboratory. Structural analysis of synthetic isomer of didemnaketal A indicates that the esters at C7 and C8 are correctly assigned, suggesting that the problems for the structural reassignment of natural didemnaketal A lie elsewhere.     

Heinz type inequalities for mappings satisfying Poisson’s equation

In this paper, we study the Heinz type inequalities for mappings satisfying Poisson’s equation. Some results generalize the ones obtained by Partyka and Sakan.     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Visual detection of Al ions using conjugated copolymer-ATP supramolecular complex

A colorimetric Al³⁺ sensor based on fluorescence recovery of a conjugated copolymer-ATP complex is proposed. An optimized ratio of two polythiophene (PT) monomers is utilized to synthesize copolymer (CP) that yielded maximized colorimetric response for Al³⁺ in deionized (DI) and tap water. The electrostatic disassembly of CP-ATP upon addition of Al³⁺ led to an evident visual color change. The lowest concentration of Al³⁺ for naked eye observation is around 4 μM, which is below the threshold levels in drinking water according to European Economic Community (EEC) standard. Besides, the proposed assay showed a similar response to Al³⁺ in tap water. The proposed methodology showed selective and sensitive detection for Al³⁺ in analytically relevant concentration ranges without involving sophisticated instrumentation, illustrating the applicability for on-site drinking water monitoring.     

Facile and green synthesis of Co3O4 nanoplates/graphene nanosheets composite for supercapacitor

Journal of Solid State Electrochemistry - A series of Co3O4 nanoplates/graphene nanosheets (GNS) composites are fabricated using a facile and green method by hydrothermal treatment and subsequent...     

Fabrication of Gene Carrier via Self-assembly of Poly[(dimethylamino)ethyl Methacrylate] and Poly(aspartic acid)-grafted-Poly(ethylene glycol)

A biocompatible complex has been prepared as gene carrier via electrostatic interaction, which is composed of a polycation, that is, poly[(dimethylamino)ethyl methacrylate] end-capped with cholesterol moiety (Chol-PDMAEMA₃₀), along with a polyanion named poly(aspartic acid)-grafted-poly(ethylene glycol) (PASP-g-PEG). The complexes have less cytotoxicity compared to the case of alone Chol-PDMAEMA₃₀ or branched polyethylenimine (PEI) system.

In the present study, biocompatible complexes have been prepared as gene carrier via electrostatic interaction, which is composed of a polycation, that is, poly[(dimethylamino)ethyl methacrylate] end-capped with cholesterol moiety (Chol-PDMAEMA₃₀), along with a polyanion named poly(aspartic acid)-grafted-poly(ethylene glycol) (PASP-g-PEG). We first synthesized polysuccinimide (PSI) via condensation polymerization of aspartic acid, and then used PEG-NH₂ to react with the partial pentacyclic rings of PSI to yield a kind of graft copolymer polysuccinimide-grafted-poly(ethylene glycol) (PSI-g-PEG). After hydrolysis of the residual succinimide units, a new biodegradable and biocompatible graft copolymer PASP-g-PEG was prepared successfully. Chol-PDMAEMA₃₀ was synthesized via oxyanion-initiated polymerization, as reported in our previous literature. We investigated the interactions between every pair among calf thymus DNA, Chol-PDMAEMA₃₀, and PASP-g-PEG by agarose gel retardation assay. The results indicate that the prepared complexes could completely bind DNA and may become more stable during systemic circulation. The complexes have less cytotoxicity compared to the case of alone Chol-PDMAEMA₃₀ or branched polyethylenimine (PEI) system. Furthermore, the physicochemical properties of the complexes were also investigated by zeta potential, transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. These biodegradable and biocompatible polymeric carriers have potential applications in gene delivery.