Synthesis and self-assembly behaviors of four-armed amphiphilic polystyrene-b-poly(N-isopropylacrylamide) copolymers

Four-armed amphiphilic block copolymers polystyrene-b-poly(N-isopropyl acrylamide) (PSt-b-PNIPAAM)₄ were synthesized by atom transfer radical polymerization (ATRP) in two steps. Star narrow dispersed polystyrene, (PSt-Br)₄, with controlled number-average molecular weight was firstly synthesized by ATRP of styrene (St) using pentaerythritol tetrakis (2-bromoisobutyrate) (4Bri-Bu) as four-armed initiator. Then, (PSt-b-PNIPAAM)₄ was prepared using (PSt-Br)₄ as macroinitiator by ATRP. The structures of (PSt-Br)₄ and (PSt-b-PNIPAAM)₄ were confirmed by characterization by nuclear magnetic resonance (¹H NMR). The apparent viscosity of the four-armed (PSt-b-PNIPAAM)₄ was significantly lower than that of the linear PSt-b-PNIPAAM with the same amount of repeat units of PSt and PNIPAAM. The self-assembly behavior of the four-armed amphiphilic block copolymers (PSt-b-PNIPAAM)₄ in mixed solution (DMF/H₂O) and the lower critical solution temperature (LCST) of the resulting micelles were investigated by scanning electron microscopy (SEM), dynamic light scattering (DLS) and UV-VIS spectroscopy. The results show that the size of the mono-dispersed spherical micelles decreased with the increment of the chain length of PNIPAAM in the block copolymers, while LCST increased.     

Coupling of ultrasound‐assisted extraction and expanded bed adsorption for simplified medicinal plant processing and its theoretical model: Extraction and enrichment of ginsenosides from Radix Ginseng as a case study

A high‐efficient and environmental‐friendly method for the preparation of ginsenosides from Radix Ginseng using the method of coupling of ultrasound‐assisted extraction with expanded bed adsorption is described. Based on the optimal extraction conditions screened by surface response methodology, ginsenosides were extracted and adsorbed, then eluted by the two‐step elution protocol. The comparison results between the coupling of ultrasound‐assisted extraction with expanded bed adsorption method and conventional method showed that the former was better than the latter in both process efficiency and greenness. The process efficiency and energy efficiency of the coupling of ultrasound‐assisted extraction with expanded bed adsorption method rapidly increased by 1.4‐fold and 18.5‐fold of the conventional method, while the environmental cost and CO₂ emission of the conventional method were 12.9‐fold and 17.0‐fold of the new method. Furthermore, the theoretical model for the extraction of targets was derived. The results revealed that the theoretical model suitably described the process of preparing ginsenosides by the coupling of ultrasound‐assisted extraction with expanded bed adsorption system.     

Separation,interconversion, and insecticidal activity of the cis‐ and trans‐isomers of novel hydrazone derivatives

A series of cis‐ and trans‐isomers of hydrazone derivatives were separated and analyzed through HPLC with diode‐array detection and HPLC‐MS/MS using ESI and ion trap MS. Two single crystals (A‐5‐1 and C‐2‐1) of the trans‐isomers were obtained and determined using X‐ray crystallography data, and the cis‐ to trans‐isomerization under different conditions was discussed. Both of the cis‐ and trans‐isomers of A‐4 and A‐5 exhibited good insecticidal activities against Plutella xylostella.     

Rapid determination of catecholamines in urine samples by nonaqueous microchip electrophoresis with LIF detection

A method was developed for the rapid separation of catecholamines by nonaqueous microchip electrophoresis (NAMCE) with LIF detection, A homemade pump‐free negative pressure sampling device was used for rapid bias‐free sampling in NAMCE, the injection time was 0.5 s and the electrophoresis separation conditions were optimized. Under the optimized conditions, the samples were separated completely in <1 min. The average migration times of the epinephrine (E), dopamine (DA), and norepinephrine (NE) were 34.26, 43.81, and 50.07 s, with an RSD of 1.05, 1.26, and 0.89% (n = 7), respectively. The linearity of the method ranged from 0.0125 to 2.0 mg/L for E and 0.025～4.0 mg/L for DA and NE, with correlation coefficients ranging between 0.9978 and 0.9986. The detection limits of E, DA, and NE were 2.5, 5.0, and 5.0 μg/L, respectively. The recoveries of E, DA, and NE in spiked urine samples were between 86 and 103%, with RSDs of 4.5～6.8% (n = 5). The proposed NAMCE with LIF detection combined with a pump‐free negative pressure sampling device is a simple, inexpensive, energy efficient, miniaturized system that can be successfully applied for the determination of catecholamines in urine samples.     

Wrinkling and Growth Mechanism of CuO Nanowires in Thermal Oxidation of Copper Foil

We report a systematic study on wrinkling and CuO nanowires （NWs） growth in the thermal oxidation of copper foil. Copper foils with thickness of 0.5 mm were thermally oxidized in air at 500℃ for 0.5-10 h. It is found that all the samples have wrinkles and the size of the wrinkles increases with the oxidation time increasing. CuO NWs can grow on both the sidehill and hilltop of wrinkle. The CuO NWs on sidehill are longer and denser than those on hilltop. The growth direction of the CuO NWs on sidehill is not vertical to the substrate but vertical to their growth surfaces. The process of wrinkling and CuO NWs growth can be divided into three stages： undulating, voiding, and cracking. The CuO NWs on both sidehill and hilltop grow at the undulating stage. However, only the CuO NWs on sidehill grow and those on hilltop stop growing at the voiding and cracking stages because of the void in hilltop. The local electric field in a wrinkle at undulating stage was calculated, and it is found that the difference of local electric field strengths between hilltop and sidehill is small, which indicates that the predominant driving force for the diffusion of Cu ion during CuO NWs growth is internal stress.     

Syntheses, structures and magnetic properties of three Co(II) coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands

Three new cobalt complexes, {[Co₅(tci)₂(bimb)₃(µ₃-O)₂(H₂O)₂]·3DMF·4H₂O} _n (1), {[Co₃(tci)₂(bib)]·2DMF·2H₂O} _n (2) and {[Co(Htci)(bpea)_0.5]·H₂O} _n (3) (H₃tci = tris(2-carboxyethyl)isocyanurate, bimb = 4,4′-bis(imidazol-1-yl)biphenyl, bib = 1,4-bis(imidazol-1-yl)benzene, bpea = 1,2-bis(4-pyridyl)ethane, DMF = N,N′-dimethylformamide), have been successfully synthesized through the assembly of Co(II) ions, H₃tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRPD). Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D → 3D structure with (6⁵·8) CdSO₄ topology. Complex 2 is built from [Co₃(µ₂-O_carboxyl)₂(CO₂)₄] clusters and linear bib ligands, displaying a two-fold parallel interpenetrated (3,8)-connected (4³)₂(4⁶·6¹⁸·8⁴) topology, while complex 3 is a 3D pillar-layered structure involving an infinite -Co-(µ₂-Ocarboxyl)(CO₂)-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indicates that besides spin-orbit coupling of Co(II) ions, there exist antiferromagnetic exchange interactions in Co₅ and Co₃ clusters of 1 and 2, respectively.     

Predicting hiCE inhibitors based upon pharmacophore models derived from the receptor and its ligands

Human intestinal carboxyl esterase (hiCE) is a drug target for ameliorating irinotecan-induced diarrhea. By reducing irinotecan-induced diarrhea, hiCE inhibitors can improve the anti-cancer efficacy of irinotecan. To find effective hiCE inhibitors, a new virtual screening protocol that combines pharmacophore models derived from the hiCE structure and its ligands has been proposed. The hiCE structure has been constructed through homology techniques using hCES1’s crystal structure. The hiCE structure was optimized via molecular dynamics simulations with the most known active hiCE inhibitors docked into the structure. An optimized pharmacophore, derived from the receptor, was then generated. A ligand-based pharmacophore was also generated from a larger set of known hiCE inhibitors. The final hiCE inhibitor predictions were based upon the virtual screening hits from both ligand-based and receptor-based pharmacophore models. The hit rates from the ligand-based and receptor-based pharmacophore models are 88% and 86%, respectively. The final hit rate is 94%. The two models are highly consistent with one another (85%). This proves that both models are reliable.     

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime: Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater.However,the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consideration.In this paper,polyvinyl alcohol functionalized with amidoxime(PVA-g-AO)has been prepared as a new adsorbent for uranium(Ⅵ)adsorption from aqueous solution.The physicochemical properties of PVA-g-AO were investigated using infrared spectroscopy(IR),scanning electron microscope(SEM),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).Results showed that the ligand monomers were successfully grafted onto the matrixes.The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form.Uranyl(U(Ⅵ))adsorption properties onto PVA-g-AO were evaluated.The adsorption of U(Ⅵ)by PVA-g-AO was fast,with an equilibrium time of less than 50 min.Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.     

Electroluminescence performances of 1,1-bis(4-(N,N-dimethylamino)phenyl)-2,3,4,5-tetraphenylsilole based polymers in three cathode architectures

A new silole monomer with two 4-(N,N-dimethylamino)phenyl substitutions on silicon atom as designed and synthesized.Three copolymers PF-N-HPS1,PF-N-HPS10 and PF-N-HPS20 were then obtained by copolymerizations of 2,7-fluorene derivatives with the silole monomer at feed ratios of 1%,10%,and 20%.Their UV-vis absorption,electrochemical,photoluminescent,and electroluminescent (EL) properties were investigated.PF-N-HPS possessed HOMO levels of 5.25-5.58 eV,and showed green emissions.Using PF-N-HPS as the emissive layer,three different polymer light-emitting diodes were fabricated as device A with ITO/PEDOT/PF-N-HPS/Al,device B with ITO/PEDOT/PF-N-HPS/Ba/Al,and device C with ITO/PEDOT/PF-N-HPS/TPBI/Ba/Al.For the device A,PF-N-HPS only showed very low EL efficiency of 0.06-0.33 cd/A,indicating that the Al cathode could not inject electron efficiently to the emissive polymers containing the 4-(N,N-dimethylamino)phenyl groups.For the device B,low work function Ba supplied better electron injections,and the EL efficiency could be improved to 0.85-1.44 cd/A.TPBI with a deep HOMO level of 6.2 eV could enhance electron transport and hole blocking.Thus modified recombinations and largely elevated EL efficiency of 4.56-7.96 cd/A were achieved for the device C.The separation of the emissive layer and metal cathode with the TPBI layer may also suppress exciton quenching at the cathode interface.